Supporting Information

The Continuum Between Hexagonal Planar and Trigonal Planar
Geometries

M. Garçon, A. Phanopoulos, G. A. Sackman, C. Richardson, A. J. P. White, R. I. Cooper,
A. J. Edwards, M. R. Crimmin*



S2 
 

 

Table of Contents 

 

1. General Experimental ........................................................................................................ 3 

2. Synthesis of Starting Materials .......................................................................................... 4 

3. Synthesis of Heterometallic Hydrides ................................................................................ 5 

4. Products from the Reaction of [PdMe2(κ2-TMEDA)] and 3a ........................................... 14 

4.1. NMR spectroscopy................................................................................................... 14 

4.2. X-ray Diffraction Study of Side-Product................................................................... 16 

5. Crystallographic Data – X-ray Diffraction ........................................................................ 17 

6. Neutron single-crystal Laue Diffraction studies ............................................................... 21 

7. Discussion of Ternary Hydrides ....................................................................................... 22 

8. Density Functional Theory Calculations .......................................................................... 23 

8.1. Computational Methods ........................................................................................... 23 

8.2. Comparison of Bonding Parameters for Model and Full Systems .......................... 24 

8.3. Molecular Orbital Analysis ....................................................................................... 26 

8.4. Symmetry Elements for the Hexagonal Planar Geometry ...................................... 30 

8.5. PES for Hexagonal and Trigonal Planar Geometries ............................................. 31 

8.6. Vibrational analysis for Hexagonal and Trigonal Planar Geometries ..................... 33 

9. XYZ Coordinates .............................................................................................................. 35 

10. References ................................................................................................................... 80 

 

 

 

  



S3 
 

1. General Experimental 

Unless otherwise specified, all manipulations were carried out using standard Schlenk and 

glovebox techniques, under inert atmosphere (nitrogen or argon). A MBRAUN Labmaster 

glovebox was employed operating with concentrations of H2O and O2 below 0.1 ppm. 

Anhydrous solvents were obtained from a Grubbs type SPS system and stored over activated 

3Å molecular sieves under inert atmosphere. Alternatively, they were dried using molecular 

sieves and degassed by freeze-pump-thaw procedures. Stable liquid organic reagents were 

dried over 3Å molecular sieves and degassed by freeze-pump-thaw cycles before use. All 

other reagents were obtained from commercial suppliers (Sigma-Aldrich, Alfa Aesar, 

Fluorochem) and used without further purification. The synthesis and characterisation of the 

β-diketiminate ligand,1 compounds 2b and 3a,2 3b3 and 6a4 have been described elsewhere. 

[1]2 was prepared by modified literature procedures as detailed below. 13CH3I5 and 13CH3Li6 

were synthesised sequentially from 13CH3OH (99 atom % 13C, Sigma-Aldrich) as described in 

the literature. [PdMe2(κ2-TMEDA)] and [Pd(13CH3)2(κ2-TMEDA)] were synthesised from 

[PdCl2(κ2-TMEDA)] and MeLi or 13CH3Li, respectively, as described.7 

1H, 2H, 13C{1H}, 31P{1H} and 195Pt NMR spectra and two-dimensional experiments (e.g. COSY, 

NOESY, DOSY, HSQC, HMBC, 1H-31P HMBC, 1H-195Pt-HMQC) were conducted in J. Young’s 

NMR tubes on BRUKER 400 MHz or 500 MHz spectrometers. Chemical shifts (δ) were 

referenced to internal solvent resonances. Data was processed using the MestReNova or 

TopSpin software packages. The coupling constants (J) are reported in Hertz (Hz). The 

following abbreviations are used to define multiplicities: s (singlet), d (doublet), t (triplet), q 

(quadruplet), quint. (quintet), sept. (septet), dd (doublet of doublets), m (multiplet), br s (broad 

signal).  

Single crystal X-ray data for compounds 2a, 4, 5 and 6b were collected using an Agilent 

Xcalibur PX Ultra A diffractometer, and the structures were refined using the SHELXTL and 

SHELX-2013 program systems.8 The Laue single-crystal neutron diffraction studies reported 

here were undertaken by mounting each crystal to the φ axis of the KOALA diffractometer 

standing at the end of the TG3 supermirror guide at the OPAL nuclear reactor, ANSTO. The 

crystals were cooled in the open flow of an Oxford Cryosystems COBRA™ 173 K nitrogen 

stream. Detection was by means of neutron sensitized ‘Niimura special’ image plates mounted 

to the fixed radius cylindrical detector drum. Details of the individual data collection and 

reduction procedures are provided in the relevant CIFs. All crystals are of low symmetry and 

wherever possible data from two separate orientations of the unit cell with respect to the φ 

axis of the instrument were recorded to ensure full coverage of the unique fraction of reciprocal 

space. 



S4 
 

2. Synthesis of Starting Materials 

 

 

Synthesis of [1]2: The ligand {(DippNCMe)2CH}H (Dipp = 2,6-di-iso-propylphenyl, 5.0 g, 12 

mmol, 1 equiv.) was dried under vacuum for 2-3h, and then dissolved in anhydrous toluene 

(ca. 60 mL). n-BuLi (7.9 mL, 1.6 M sol. in hexanes, 12.6 mmol, 1.05 equiv.) was then added 

dropwise at -78 °C with a syringe. The reaction was allowed to reach 25 °C and was stirred 

for a further 1h. MeMgBr (4.2 mL, 3 M sol. in diethyl ether, 12.6 mmol, 1.05 equiv.) was then 

added dropwise (during around 5 minutes) via syringe at 0°C. The mixture was stirred at 25 

ºC overnight. It was then filtered via cannula and the solvent removed in vacuo to afford a 

colourless solid, which was then transferred to the glovebox and washed with n-hexane (ca. 

10 mL). The solid was washed again with toluene (ca. 5 mL) to remove a small impurityi to 

afford [{(DippNCMe)2CH}Mg(-Me)]2 as a colourless solid (3.97 g, 4.3 mmol, 72% yield). The 

product was used in the next step without further purification. 

In a glovebox, [{(DippNCMe)2CH}Mg(-Me)]2 (500 mg, 0.55 mmol, 1 equiv.)ii was suspended 

in dry toluene (ca. 20 mL) in a J. Young ampoule and PhSiH3 (0.202 mL, 1.64 mmol, 1.5 

equiv.) was subsequently added. The ampoule was taken outside the glovebox and the 

mixture was stirred at 80 °C for 2 days. The white suspension becomes a colourless solution. 

The solution was cooled down, transferred to a Schlenk flask and concentrated in vacuo until 

precipitation started. The mixture was left in the freezer overnight, filtered via cannula (the 

discarded solid was a mixture of [1]2 and unreacted [{(DippNCMe)2CH}Mg(-Me)]2) and the 

solvent was evaporated. The residue was washed with n-hexane to afford the desired product 

[1]2 as an off-white solid (206 mg, 0.23 mmol, 43% yield).  

1H-NMR (400 MHz, C6D6) δ (ppm): 0.96 (d, 3JH-H = 6.3 Hz, 24H, CHMe2), 1.10 (d, 3JH-H = 6.4 

Hz, 24H, CHMe2), 1.48 (s, 12H, Me), 3.05 (sept, 3JH-H = 7.2 Hz, 8H, CHMe2), 4.03 (s, 2H, Mg-

H), 4.83 (s, 2H, β-CH), 6.97 – 7.13 (m, 12H, Ar). Data are consistent with those previously 

reported.9  

 
i It is important to use relatively fresh MeMgBr, as old solutions will increase the amount of impurities, hindering 
purification.  
ii The reaction with phenylsilane can be successfully scaled up six-fold. A higher yield was obtained. 



S5 
 

3. Synthesis of Heterometallic Hydrides 

 

Synthesis of 2a: In a J. Young’s NMR tube, [1]2 (10 mg, 0.011 mmol, 1.0 equiv.) and [Pd(-

dcpe)]2 (12 mg, 0.011 mmol, 1.0 equiv.) were dissolved in benzene (1 mL). The resulting 

solution was left at 25 °C for 4 days. The precipitate was filtered off through a glass fibre and 

the volatiles were removed in vacuo. The crude product was dissolved in a small amount of 

n-hexane (0.5 mL), and the solution was stored at –35 °C to afford crystals of 2a. The desired 

product 2a was isolated as yellow crystals (15 mg, 0.015 mmol, 68% yield).  

1H NMR (400 MHz, C6D6) δ (ppm): –0.55 (t, 2JH–P = 47 Hz, 1H, PdH), 0.93–1.73 (series of 

overlapping m, Cy), 1.23 (d, 3JH-H = 7.1 Hz, 12H, CHMe2), 1.35 (d, 3JH-P = 9.6 Hz, 4H, CH2CH2), 

1.45 (d, 3JH-H = 6.5 Hz, 12H, CHMe2), 1.76 (s, 6H, Me), 3.50 (sept, 3JH-H = 6.9 Hz, 4H, CHMe2), 

5.03 (s, 1H, β-CH), 7.03–7.13 (series of overlapping m, 6H, Ar).  

T1 relaxation time (PdH signal, 298 K): 2.0 s.  

13C{1H} NMR (126 MHz, C6H6) δ (ppm): 23.2–23.5 (m, 2xCH2), 24.0 (2xCH3), 24.4 (4xCH3), 

26.1 (4xCH3), 26.7 (CH2, Cy), 27.7 (d, JC-P = 8 Hz, CH2, Cy), 27.8 (d, JC-P = 13 Hz, CH2, Cy), 

28.4 (4xCH), 29.0 (CH2, Cy), 30.2 (d, JC-P = 11 Hz, CH2, Cy), 36.2 (br s, 4xCH, Cy), 95.0 (CH), 

123.6 (4xCH), 125.0 (2xCH), 142.5 (4xC), 145.5 (2xC), 167.8 (2xC).  

31P{1H} NMR (202 MHz, C6H6) δ (ppm): 50.4 (br s).  

ATR IR (cm−1): 3059, 2958, 2922, 2851, 1620, 1549, 1458, 1438, 1362, 1322, 1273, 1173, 

1101, 758. 

Due to the thermal instability of this compound CHN analysis was not obtained. 

 

 

  



S6 
 

 

Synthesis of 4: In a J. Young’s NMR tube, 3a (40 mg, 0.083 mmol, 3.0 equiv.) was partially 

dissolved in benzene (0.6 mL). A solution of [PdMe2(κ2-TMEDA)] (7 mg, 0.028 mmol, 1.0 

equiv.) in benzene (0.6 mL) was added, the tube sealed and inverted three times. The pale-

yellow solution was allowed to stand at 25 °C for 25 minutes, during which time bubbles were 

observed and the colour changed to dark yellow/brown. The solvent and volatiles were 

removed in vacuo for 45 minutes, before the resultant solid was treated with n-pentane (1 mL), 

filtered through a glass fibre, and the solution was stored at –35 °C to afford crystals. The 

desired product 4 was isolated as yellow block crystals (14.4 mg, 0.0064 mmol, 46% yield). 

1H NMR (400 MHz, C6D6) δ (ppm): –4.53 (s, 4H, PdH), 1.18 (d, 3JH-H = 6.9 Hz, 48H, CHMe2), 

1.20 (d, 3JH-H = 6.9 Hz, 48H, CHMe2), 1.58 (s, 24H, Me), 2.12 (s, 12H, NMe2), 2.36 (s, 4H, 

CH2CH2), 3.17 (sept, 3JH-H = 6.9 Hz, 16H, CHMe2), 4.85 (s, 4H, β-CH), 7.12–7.20 (series of 

overlapping m, 6H, Ar). 

T1 relaxation time (PdH signal, 298 K): 1.3 s 

DOSY: TMEDA resonances diffuse (Dave = 1.70 x 10–9 m2/s) separately to β-diketiminate unit 

(Dave = 7.05 x 10–10 m2/s). 

Variable temperature experiments. 1H NMR spectra in toluene-d8 were recorded between 

298 and 198 K, with additional spectra measured in 5 K steps between 223 and 198 K. A 

broadening and eventual splitting of the PdH signal was observed, with a coalescence 

temperature of 213 K. The non-uniform splitting of the signal (1.00:1.37 ratio of signals at –

5.53 ppm and –4.94 ppm, respectively, at 198 K) suggests this is due to a slowing of an 

equilibrium between a TMEDA-bound and -unbound species, rather than freezing out of 

inequivalent hydride ligands. These data were modelled using the DNMR package within 

Topspin. The peak positions, intensities and molecular coefficients were freely iterated during 

the model, while line broadening was held at 10 Hz. A rate constant was extracted from each 

spectrum between 223 and 198 K, and Eyring analysis suggests an activation free energy of 

8.6 kcal mol–1 for this process. 



S7 
 

13C{1H} NMR (101 MHz, C6H6) δ (ppm): 24.3 (s, Me), 25.5 (s, CHMe2), 28.4 (s, CHMe2), 46.1 

(s, NMe2), 58.5 (s, CH2CH2), 96.6 (s, β-CH), 123.9 (s, meta/para-Ar), 125.8 (s, meta/para-Ar), 

141.8 (s, ipso-Ar), 142.8 (s, ortho-Ar), 167.2 (s, C=N). 

ATR IR (cm−1): 2963, 2922, 2867, 2821, 2775, 1933 (Pd–H), 1918 (Pd–H), 1869 (Pd–H), 1859 

(Pd–H), 1522, 1435, 1383, 1314, 1266, 1252, 1177, 1100, 1020, 936, 854, 796, 760. 

Anal. Calc. (C122H184N10Pd2Zn4): C, 64.69; H, 8.19; N, 6.18. Found: C, 65.70; H, 8.49; N, 5.94.  

   

 

Figure S1. 1H DOSY NMR spectrum of 4 showing different diffusion coefficients for TMEDA and 
ligand fragments. 

 

-6-5-4-3-2-10123456789
δ/ppm

1×10
-10

1×10
-9

1×10
-8

m
2
/s

-5.5-5.0-4.5-4.0-3.5
δ/ppm

1.0×10
-9

1.5×10
-9

2.0×10
-9

2.5×10
-9

m
2
/s



S8 
 

        

Figure S2. Experimental variable temperature 1H NMR spectra showing the hydride region of 4 (left) 
and Eyring analysis of modelled data, including a schematic of the equilibrium being studied (right). 

 

 

  

-7.8-7.6-7.4-7.2-7.0-6.8-6.6-6.4-6.2-6.0-5.8-5.6-5.4-5.2-5.0-4.8-4.6-4.4-4.2-4.0-3.8-3.6-3.4-3.2-3.0-2.8
δ/ppm

223 K 

218 K 

213 K 

208 K 

203 K 

198 K 



S9 
 

 

Synthesis of 5:  Can be synthesised from isolated crystals of 4 (Method A), or in a one-pot 

reaction starting from 3a, [PdMe2(κ2-TMEDA)] and 3b (Method B). 

Method A. In a J. Young’s NMR tube, isolated crystals of 4 (3.4 mg, 0.0015 mmol, 1.0 equiv.) 

were dissolved in benzene (0.5 mL). A suspension of 3b (2.4 mg, 0.0060 mmol, 4.0 equiv.) in 

benzene (0.5 mL) was added, and the tube sealed and inverted three times. The mixture was 

allowed to stand at 25 °C for 1 h, during which time the initial pale-yellow solution turns 

colourless. The solvent and volatiles were removed in vacuo for 1 h, before the resultant solid 

was treated with n-pentane (1 mL), filtered through a glass fibre, and the solution was stored 

at –35 °C to afford crystals. The crystals were discardediii and the supernatant re-stored at –

35 °C to afford a second batch of crystals, which are again discarded. iii The supernatant was 

evaporated, and the resultant powder washed swiftly with cold (–35 °C) n-pentane and dried 

in vacuo. The remaining powder contains an enriched mixture of 5 with some 

[{(DippNCMe)2CH}ZnMe] (Dipp = 2,6-di-iso-propylphenyl) carried through from synthesis of 4 

and 3a still present. 

Method B. In a J. Young’s NMR tube, 3a (20.2 mg, 0.042 mmol, 3.5 equiv.) was dissolved in 

benzene (0.5 mL). A solution of [PdMe2(κ2-TMEDA)] (3 mg, 0.012 mmol, 1.0 equiv.) in 

benzene (0.2 mL) was added, the tube sealed and inverted three times. The pale-yellow 

solution was allowed to stand at 25 °C for 20 minutes, during which time bubbles were 

observed. A suspension of 3b (9.5 mg, 0.024 mmol, 2.0 equiv.) in benzene (0.3 mL) was 

added, and the tube sealed and inverted three times. The mixture was allowed to stand at 25 

°C for 1 h, during which time the initial pale-yellow solution turns colourless. The subsequent 

work-up is identical to Method A. The resultant colourless powder (3.7 mg) was found to 

primarily consist of a mixture of [{(DippNCMe)2CH}ZnMe] and 5 in a 60:40 ratio (Figures S3). 

NMR yield of 5 can be calculated as >0.0017 mmol, >14%.iv 

 
iii  Note a very small amount of product 5 does crystallise, and can be separated from crystals of 
[{(DippNCMe)2CH}ZnMe] (major species), 3a and 3b manually under a microscope, differentiated by their slightly 
different morphologies: trapezoidal colourless blocks of 5 vs. more cubic colourless blocks of the other species 
present. 
iv Note this is a minor product of the reaction (hence the convoluted purification and low yield).  



S10 
 

1H NMR (400 MHz, C6H6 w/ C6D6 lock tube) δ (ppm) : –1.26 ppm (s, PdH3), 0.79 (d, 3JHH = 

6.8 Hz, CHMe2), 1.21 (d, 3JHH = 6.8 Hz, CHMe2), 1.51 (s, MeMes), 1.66 (s, MeDipp), 1.93 (s, 

ortho-MeMes), 2.30 (s, para-MeMes), 3.14 (hept, 3JHH = 6.8 Hz, CHMe2), 4.82 (s, β-CHMes), 4.92 

(s, β-CHDipp), 6.76 (s, meta-CHMes), other aromatic peaks overlapping with C6H6 solvent. 

DOSY: Diffusion coefficient for 5 (Dave = 5.39 x 10–10 m2/s) is smaller than corresponding 

diffusion coefficients for 3a (Dave = 8.20 x 10–10 m2/s) and 4 (Dave = 7.05 x 10–10 m2/s) in the 

same solvent at similar concentrations. These data imply hydrodynamic radii of 6.34 Å, 4.17 

Å and 5.15 Å, respectively, but with a large degree of error associated with the assumptions 

made during analysis with the Stokes-Einstein equation. 

13C{1H} NMR (101 MHz, C6H6 w/ C6D6 lock tube) δ (ppm): 19.26 (s, CH3
meta-Mes), 21.08 (s, 

CH3
para-Mes), 23.12 (s, CH3

BDI,Mes), 24.60 (s, CH3
BDI,Dipp), 25.59 (s, CH3

iPr,Dipp), 28.34 (s, CHiPr,Dipp), 

34.44 (CH3
iPr,Dipp), 96.45 (CHBDI,Mes), 96.69 (CHBDI,Dipp), 123.44 (s, CHmeta-Dipp), 129.42 (s, CHmeta-

Mes), 131.32 (s, Cipso-Dipp), 131.90 (s, Cipso-Mes), 142.58 (s, Cortho-Dipp), 145.42 (s, Cpara-Mes), 145.84 

(s, Cortho-Mes), 166.24 (s, C=NBDI,Mes), 167.11 (s, C=NBDI,Dipp). 

ATR IR (cm−1): 2960, 2922, 2863, 2821, 2775, 1804 (Pd–H), 1521, 1439, 1387, 1319, 1260, 

1200, 1178, 1148, 1103, 1021, 932, 857, 798, 753. 

Due to the thermal instability of this compound CHN analysis was not obtained. 

 

Product 5 is not stable in solution at room temperature, and has completely decomposed after 

several hours. Over time the signals for [{(DippNCMe)2CH}ZnMe] become more intense 

compared to 5. The presence of a single hydride resonance observed for 5 (vide infra) 

suggests the species is fluxional on the NMR time-scale and hence each resonance 

associated with 5 will be timed-average. In solution, 5 is likely to exist as a mixture of 

complexes ranging from those with three {(DippNCMe)2CH}Zn to three {(MesNCMe)2CH}Zn 

ligands, as well as mixtures thereof. Computational analysis at the BS3 level (vide infra) 

reveals that moving from zero to three {(MesNCMe)2CH}Zn ligands, while displacing 

{(DippNCMe)2CH}Zn ligands, is exergonic by –3.7 (1 displaced), –15.8 (2 displaced) and –

23.5 kcal mol–1 (3 displaced). The analogous species to 5 with three {(MesNCMe)2CH}Zn 

ligands is computed to be the lowest energy. The crystal analysed by X-ray diffraction was 

found to contain one {(DippNCMe)2CH}Zn and two {(MesNCMe)2CH}Zn ligands. As such, and 

in addition to the low stability of the complex, it was not possible to assign accurate integration 

data to the observed resonances. However, resonances associated with both 

{(DippNCMe)2CH}Zn and {(MesNCMe)2CH}Zn ligands were observed that are not associated 

with [{(DippNCMe)2CH}ZnMe]. 



S11 
 

 

 

Figure S3. 1H NMR spectrum of a 40:60 mixture of 5 and [{(DippNCMe)2CH}ZnMe]. Identification of 

the resonances for 5 (▲) was aided by excluding those of [{(DippNCMe)2CH}ZnMe] (■) which can be 

obtained separately as analytically pure crystals, and from 2D correlation experiments. 

  

▲ 

▲ 

▲ 

▲ 

▲ 

▲ 

▲ 

▲ 

▲ 

▲ 

■ 

■ 

■ 

■ 

■ 
▲ 



S12 
 

 

 

Synthesis of 6b: In an ampoule, [1]2 (207.6 mg, 0.234 mmol, 2.0 equiv.) and [PtMe2(κ2-

TMEDA)] (40 mg, 0.117 mmol, 1.0 equiv.) were dissolved in benzene (5 mL). The resulting 

solution was stirred at 25 °C for 4 days. The ampoule was then taken into the glovebox and 

the precipitate allowed to settle as a sediment. The supernatant was decanted, filtered through 

a glass fibre and the volatiles removed in vacuo. The residue was washed with cold n-hexane 

(1 mL). The residue was then extracted with cold toluene (1 mL), filtered through a glass fibre 

and the volatiles evaporated. The residue was then dissolved in a 1:1 n-hexane:toluene 

mixture (0.5 mL) and left at –35 °C. A small amount of solids precipitated out, which was 

discarded. The filtrate was then evaporated and washed swiftly with n-hexane (2 x 1 mL, at 

25 °C). The remaining solid was dried in vacuo and shown to be the desired product. 6b was 

isolated as a white solid (22 mg, 0.014 mmol, 12% yield).v 

1H NMR (400 MHz, C6D6) δ (ppm): –2.88 (s, 1JH-Pt = 1080 Hz (satellites), 3H, PtH3), 0.98 (d, 

3JH-H = 6.8 Hz, 36H, CHMe2), 1.20 (d, 3JH-H = 6.9 Hz, 36H, CHMe2), 1.54 (s, 18H, Me), 3.14 

(sept, 3JH-H = 6.8 Hz, 12H, CHMe2), 4.87 (s, 3H, β-CH), 7.03–7.13 (m, 18H, Ar).  

T1 relaxation time (PtH3 signal, 298 K):  1.0 s.  

13C{1H} NMR (101 MHz, C6D6) δ (ppm): 24.2 (12xCH3), 24.7 (6xCH3), 25.7 (12xCH3), 28.5 

(12xCH), 96.2 (3xCH), 123.9 (12xCH), 125.4 (6xCH), 142.5 (12xC), 145.9 (6xC), 169.2 (6xC).  

195Pt NMR (108 Hz, C6H6) δ (ppm): –6159.1 (q, 1JH-Pt = 1080 Hz).  

ATR IR (cm−1): 3060, 2960, 2926, 2866, 1705, 1621, 1551, 1461, 1439, 1405, 1364, 1320, 

1260, 1174, 1103, 1018, 787, 757. 

 
v Note this is a minor product of the reaction (hence the convoluted purification and low yield).  



S13 
 

  

Figure S4. Stacked 195Pt NMR spectra showing the 1H coupled (top) and decoupled (bottom) spectra 
of 6b. 

 

 

  

-6260-6250-6240-6230-6220-6210-6200-6190-6180-6170-6160-6150-6140-6130-6120-6110-6100-6090-6080-6070-6060
δ/ppm

195Pt NMR 

195Pt{1H} NMR 



S14 
 

4. Products from the Reaction of [PdMe2(κ2-TMEDA)] and 3a 

4.1. NMR spectroscopy 

 

In situ 1H NMR spectra recorded for the reaction between [PdMe2(κ2-TMEDA)] and 3a show 

the formation of two species with a distinct high-field resonances: the Pd-containing species 

4 (–4.53 ppm), and another species assigned as the product of a ligand exchange reaction 

between Pd and Zn (–0.66 ppm). The exchange of a Pd–Me and a Zn–H ligand result in the 

formation a stable [{(DippNCMe)2CH}ZnMe] (Dipp = 2,6-di-iso-propylphenyl) complex. A 

labelling experiment was performed where 13C-labelled [Pd(13CH3)2(κ2-TMEDA)]6,7 was 

reacted with 3a. In a J. Young NMR tube, a solution of [Pd(13CH3)2(κ2-TMEDA)] (4 mg, 0.0157 

mmol, 1 equiv.) in C6H6 (0.5 mL) was added to a solution of 3a (22.8 mg, 0.0471 mmol, 3 

equiv.) in C6H6 (0.5 mL). The resultant in situ 1H NMR spectrum shows the formation of two 

species that incorporate the 13C-label. These were assigned as [{(DippNCMe)2CH}Zn(13CH3)] 

(–0.66 ppm, 1JCH = 121 Hz) and 13CH4 (0.16 ppm, 1JCH = 126 Hz), with both showing 

corresponding cross-peaks to intense 13C resonances in a HSQC experiment. The reaction 

between [PdMe2(κ2-TMEDA)] and 3a clearly results in both ligand exchange and reductive 

elimination processes prior to formation of 4. 

 

Figure S5. 1H NMR spectrum of reaction mixture between [Pd(13CH3)2(TMEDA)] and 3a. 

-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.5
δ/ppm

-0
.8

1

-0
.5

1

0
.0

0

0
.3

2

13CH4 

Zn–13CH3 



S15 
 

 

 

Figure S6. 13C{1H} NMR spectrum of reaction mixture between [Pd(13CH3)2(TMEDA)] and 3a. 

 

 

Figure S7. 1H-13C HSQC NMR spectrum of reaction mixture between [Pd(13CH3)2(κ2-TMEDA)] and 2. 

-200-180-160-140-120-100-80-60-40-20020406080100120140160180200
δ/ppm

-1
6
.8

8

-4
.7

7

-7-6-5-4-3-2-10123456789101112131415161718
δ/ppm

-50

0

50

100

150

δ
/p

p
m

{0.16,-4.83}

{-0.66,-16.87}

13CH4 

Zn–13CH3 



S16 
 

[{(DippNCMe)2CH}ZnMe] has been previously reported via a metathesis reaction between 

[{(DippNCMe)2CH}ZnI] and MeLi.10 The analogous reaction between [PdMe2(κ2-TMEDA)] and 

[{(MesNCMe)2CH}ZnH]3 (Mes = 2,4,6-trimethylphenyl) also resulted in Pd–Me and Zn–H 

ligand exchange, forming the corresponding [{(MesNCMe)2CH}ZnMe] complex. In this case, 

the high-field Zn–Me resonance was observed at –0.61 ppm, and gave identical NMR data to 

those previously reported for this complex.11 

 

Products formed from the reaction between [PdMe2(κ2-TMEDA)] and 3a are also capable of 

undergoing solvent C–H activation at higher temperatures. Formation of 

[{(DippNCMe)2CH}ZnPh]2,9 from activation of the benzene solvent is observed by 1H NMR 

spectroscopy if the reaction mixture is heated to 50 °C. 

 

4.2. X-ray Diffraction Study of Side-Product 

 

Two distinct products can be crystallized from the reaction between [PdMe2(κ2-TMEDA)] and 

3a. Larger pale yellow block crystals of 4 and smaller colourless crystals can be separated by 

hand under a microscope. X-ray diffraction experiments undertaken with the colourless 

crystals were resolved to show a dimeric structure with two [{(DippNCMe)2CH}Zn] units, but 

further analysis was inconclusive due to unassignable electron density (max peak 8.3, R1 = 

18.55%, GooF = 1.581) between the two Zn centers. This structure was persistent across 

several crystals that were analysed, and appears to be a mixture of different species. The 

analogous [{(MesNCMe)2CH}ZnMe] species was isolated from the reaction between 

[PdMe2(κ2-TMEDA)] and 3b, and afforded crystals suitable for X-ray diffraction which 

confirmed the structure. The [{(MesNCMe)2CH}ZnMe] complex has been previously reported 

and gives identical data to the crystals obtained here.12 

  



S17 
 

5. Crystallographic Data – X-ray Diffraction 

Table S1. Crystal data, data collection and refinement parameters for the structures of 2a, 4, 5 and 
6b 

data 2a 4 5 6b 

formula C55H90MgN2P2Pd C122H184N10Pd2Z

n4 

C75H102N6PdZn3 C87H126Mg3N6Pt 

solvent 0.5(C6H14) C6H14 C6H14 C7H8·C6H14 

formula weight 1015.02 2351.23 1476.30 1702.26 

colour, habit 
yellow platy 

needles 
yellow blocks colourless 

blocky needles 
colourless 
needles 

temperature / K 173 173 173 173 

crystal system triclinic monoclinic monoclinic monoclinic 

space group P–1 (no. 2) P21/n (no. 14) C2/c (no. 15) P21/c (no. 14) 

 a / Å 11.9440(4) 14.6246(5) 25.5811(8) 16.2798(5) 

 b / Å 12.0368(6) 16.6683(5) 13.9813(5) 13.0600(5) 

 c / Å 22.8595(9) 26.2662(8) 45.002(3) 45.8501(10) 

 α / deg 91.871(4) 90 90 90 

 β / deg 104.635(3) 103.526(3) 102.049(4) 93.226(2) 

 γ / deg 112.172(4) 90 90 90 

V / Å3 2914.5(2) 6225.2(3) 15740.7(14) 9732.9(5) 

Z 2 2 8 4 

Dc / g cm–3 1.157 1.254 1.246 1.162 

radiation used Cu-Kα Cu-Kα Cu-Kα Cu-Kα 

μ / mm–1 3.444 1.091 3.175 3.220 

no. of unique reflns     

 measured (Rint) 11034 (0.0388) 12392 (0.0330) 15159 (0.0337) 18623 (0.0424) 

 obs, |Fo| > 4σ(|Fo|) 9204 8972 13010 14088 

completeness (%) [a] 98.0 99.1 98.8 98.7 

no. of variables 613 680 873 951 

R1(obs), wR2(all) [b] 0.0353, 0.0893 0.0378, 0.0790 0.0479, 0.1108 0.0376, 0.0897 

CCDC code 2107421 2107423 2150654 2107426 

[a] Completeness to 0.84 Å resolution. [b] R1 = Σ||Fo| – |Fc||/Σ|Fo|; wR2 = {Σ[w(Fo
2 – Fc

2)2] / Σ[w(Fo
2)2]}1/2; w–1 = 

σ2(Fo
2) + (aP)2 + bP. 

 

 

 

 

 

 

 



S18 
 

X-ray crystal structure of 2a. The C61-based included hexane solvent molecule in the 

structure of 2a was found to be disordered across a centre of symmetry, and two unique 

orientations were identified of ca. 26 and 24% occupancy (with two further orientations of the 

same occupancies being generated by operation of the inversion centre). The geometries of 

the two unique orientations were optimised, the thermal parameters of adjacent atoms were 

restrained to be similar, and all the atoms of both unique orientations were refined isotropically. 

The Pd–H–Mg bridging hydrogen atom was located from a ΔF map and refined freely. 

X-ray crystal structure of 4. The structure of 4 was found to sit across a centre of symmetry 

at the middle of the central C–C bond of the bridging N006-based TMEDA ligand. The C01-

based included hexane solvent molecule was found to be disordered across a centre of 

symmetry, with one unique orientation identified. The geometries of the hexane solvent was 

optimised and refined anisotropically. The Pd–H–Zn bridging hydrogen atoms were located 

from a ΔF map and refined freely. 

X-ray crystal structure of 5. The C21- and C33-based iso-propyl groups in the structure of 

5 were both found to be disordered and in each case two orientations were identified, of ca. 

66:34 and 57:43%, respectively. The geometries of each pair of orientations were optimised, 

the thermal parameters of adjacent atoms were restrained to be similar, and both pairs of 

orientations were refined anisotropically. The C86-based included solvent molecule was found 

to sit in one position and was refined anisotropically. Pd–H–Zn bridging hydrogen atoms were 

located from a ΔF map and refined freely. 

X-ray crystal structure of 6b. The C12-, C27-, and C42-based iso-propyl groups in the 

structure of 6b were all found to be disordered and in each case two orientations were 

identified, of ca. 51:49, 54:46 and 87:13% occupancy respectively. The geometries of each 

pair of orientations were optimised, the thermal parameters of adjacent atoms were restrained 

to be similar, and only the non-hydrogen atoms of the major occupancy orientations were 

refined anisotropically (those of the minor occupancy orientations were refined isotropically). 

The included solvent was found to be highly disordered, and the best approach to handling 

this diffuse electron density was found to be the SQUEEZE routine of PLATON. 13  This 

suggested a total of 417 electrons per unit cell, equivalent to 104.3 electrons per asymmetric 

unit. Before the use of SQUEEZE the solvent most resembled a 1:1 mixture of toluene (C7H8, 

50 electrons) and hexane (C6H14, 50 electrons), and one toluene and one hexane molecule 

corresponds to 100 electrons, so this was used as the solvent present. As a result, the atom 

list for the asymmetric unit is low by C7H8 + C6H14 = C13H22 (and that for the unit cell low by 

C52H88) compared to what is actually presumed to be present. The three unique Pt–H–Mg 

bridging hydrogen atoms were all located from ΔF maps and refined freely. 



S19 
 

 

Figure S8. Structure of 2a. Solvent and selected hydrogens removed for clarity. Thermal ellipsoids 
drawn at 50% probability. 

 

 

Figure S9. Structure of 4. Solvent and selected hydrogens removed for clarity. Thermal ellipsoids 
drawn at 50% probability. 



S20 
 

 

Figure S10. Structure of 5. Solvent and selected hydrogens removed for clarity. Thermal ellipsoids 
drawn at 50% probability. 

 

 

Figure S11. Structure of 6b. Solvent and selected hydrogens removed for clarity. Thermal ellipsoids 
drawn at 50% probability. 



S21 
 

6. Neutron single-crystal Laue Diffraction studies 

Crystals of 2a arrived to ANSTO via air courier and data suitable for structural analysis were 

collected.   

The crystal of 2a (yellow needle 0.2 x 0.4 x 1.4 mm3) selected for data collection was the 

largest available quality specimen and ultimately proved to be a new polymorph of the 

compound, thus, the unit cell and crystal symmetry were not known at the time of the 

experiment. 21 x 10000s exposure Laue neutron diffraction images (the crystal was close to 

the minimum viable size for a unit cell of this volume) with an interframe rotation of 17o about 

φ were recorded from a single setting of the sample with respect to the φ axis. It has not been 

possible to acquire the additional data from a second setting of the crystal which would be 

preferable due to the actual low symmetry unit cell as additional beamtime has not been 

available. 

Data reduction by means of the LaueG14 suite incorporating ArgonneBoxes15  to the resolution 

of the observed pattern (1.1 Å) with all uniquely indexable reciprocal lattice points for all 

wavelengths 0.85 ≤ λ < 1.7Å included in the integration and normalization. The overall R int for 

all data extracted in this manner is, as is typical for such experiments, meaningless due to the 

large number of very weak data and the inherently high background in the neutron Laue 

experiment whereas Rint for the 4σ data [7.7(6.6) 18460 reflections 2832 I > 4σI] demonstrates 

that the merging of data is valid. Structure refinement16 commenced from the X-ray model 

coordinates and after scale factor refinement only, a difference map phased on the non-

hydrogen atom positions revealed all the hydrogen atom sites for the molecule of interest. A 

full-matrix least-squares refinement on F of all atomic sites modelled with anisotropic 

displacement parameters for non-hydrogen atoms and the metal bonded hydrides, with 

remaining hydrogens isotropic and using a Chebychev polynomial weighting scheme (3 term) 

converged to: R = 10.9%, Rw = 13.7% and S = 0.97 for 1400 parameters, 1364 restraints and 

1534 observations I ≥ 3σI. At convergence, the difference density maps were featureless at 

+/- ~0.9fm Å3 for 2a well below the value corresponding to any atom of this structure.  



S22 
 

7. Discussion of Ternary Hydrides 

Several ionic ternary hydrides have been characterised by neutron diffraction including 

[Na2PdH2], [NaBaPdD3] and [K2PdH4].17,18 Upon first inspection, these species bear some 

resemblance to the complexes reported herein and hence a critical comparison might be 

informative. These species possess linear, trigonal planar and square planar geometries at 

the transition metal, respectively (Figure S12). For example, the closest point of comparison 

for the hexagonal planar species 6a or 6b is [NaBaPdD3]. [NaBaPdD3] contains a trigonal 

planar Pd centre with a Pd–D bond distance of 1.719(8) Å.19 The Pd---Na distance of 3.810(1) 

Å is well beyond the covalent radii (Pauling, 2.85 Å; Pyykkö, 2.75 Å). The Na atoms sit outside 

the trigonal plane and interact exclusively through bridging hydride interactions. The barium 

atoms also sit outside the trigonal plane being located in an axial position. The Pd–Ba distance 

of 3.041(1) Å is long but in a reasonable range for the covalent radii (Pauling, 3.26 Å; Pyykkö, 

3.16 Å). While it is difficult to rule out a direct metal---metal interaction in this species it is 

clearly not one that would result in a hexagonal planar geometry. Similarly, although [Na2PdH2] 

contains a linear H–Pd–H motif related to that found in 4 and [K2PdH4] contains a square 

planar [PdH4]2– unit, in both cases the s-block counterions do not approach the transition 

metal20,21 and are located at remote sites in crystal lattice. For comparison the Pd–H bond 

lengths in [Na2PdH2] and [K2PdH4] are 1.68 and 1.625(8) Å, respectively.16 The bonding in 

these ternary hydrides is likely dominated by an ionic interaction between the {PdHn}n– and M+ 

or M2+ fragments with limited or no interaction between the metals themselves. As such it is 

reasonable to conclude that the structures of 2, 5 and 6 are not identical to those known from 

ionic metal salts as both the geometries and short metal---metal distances are inconsistent 

with those established for ternary hydrides. 

 

Figure S12. Reported neutron diffraction structures of unit cells containing linear, trigonal and square 
planar palladium hydride arrangements. 

  



S23 
 

8. Density Functional Theory Calculations 

8.1. Computational Methods 

DFT calculations were run using Gaussian 09 (Revision D.01)22 and Gaussian 1623 using the 

B97X hybrid exchange-correlation functional.24 NBO analysis was performed using NBO 

6.0.25 QTAIM analysis was conducted using the AIMAll package.26 Data are presented from 

veryfine mesh calculations but there are no differences in the appearance of bcps when 

calculations were run with a superfine or ultrafine mesh. Standard cut-offs for plotting the data 

with AIMAll were used. Non-covalent interactions were analysed using the NCIPLOT 3.0 

program.27  Geometry optimisations were performed without symmetry constraints, unless 

otherwise specified, and the nature of the stationary points was confirmed as minima by 

frequency calculations (no imaginary frequencies). The default numerical integration grid was 

improved using a pruned grid with 99 radial shells and 590 angular points per shell 

(int=ultrafine). It should be noted that for the geometry and bonding analysis performed in this 

work, the use of dispersion or solvent corrections was deemed unnecessary.  

The level of theory used has previously been benchmarked in our group and shown to 

reproduce accurately the experimental results.2,4 Different basis sets (BS1-4) were used as 

detailed. Geometry optimisations and population analyses on the complexes were performed 

mainly using BS1. Geometry optimisation of complex 6b with BS1 did not accurately 

reproduce the experimentally observed Mg–H distances, likely due to the flat nature of the 

PES. Therefore, the optimisation and population analysis of 6b was performed using a slightly 

modified basis set, BS2. Optimisation and bonding analysis of the model systems were 

performed using the larger basis set, BS3, which includes quadruple-ξ functions for Mg and 

Zn. Finally, wavefunction generation for QTAIM inputs were generated using BS4. Initially 

single-point calculations for population analyses for all full structures were performed with this 

basis set as well, but the systems were found to be too big. Bonding analysis was carried out 

for 1 and 3a using BS1, BS3 and BS4, and for 2a and 2b using BS1 and BS4, with no 

significant change (±0.03) in values observed (see Table S2). Bonding analysis using BS1 is 

discussed in the paper. 

BS1 was built as follows.28 The SDD effective core potential was used for all metals (SDDAll). 

The split-valence 6-31G(d) basis set was used for C and H atoms. The basis set for metal 

hydrides was expanded by adding one extra set of diffuse functions and three sets of p- and 

one set of d- polarisation functions, i.e. formally [6-31++G(d,3pd)]. The triple-ξ 6-311+G* basis 

set was used for heteroatoms. 



S24 
 

BS2 was built as follows. The SDD effective core potential was used for all metals (SDDAll). 

The split-valence 6-31G(d,p) basis set was used for C and H atoms, and the triple-ξ 6-311+G* 

basis set was used for heteroatoms. The metal hydrides used the same expanded basis set 

as BS1, formally [6-31++G(d,3pd)]. 

BS3 was built as follows. Pd and Pt were described with the SDD effective core potential, 

while the other atoms (C, H, N and P) including metals (Mg or Zn) were described using 

Ahlrichs quadruple-ξ basis set def2-QZVPP.29 

BS4 was built as follows. Pd and Pt were described with the SDD effective core potential, 

while the other atoms (C, H, N and P) including metals (Mg or Zn) were described using 

Ahlrichs triplet-ξ basis set def2-TZVPP.29 

 

 

8.2. Comparison of Bonding Parameters for Model and Full 

Systems 

 

 

Table S2. Comparison of NPA charges and Wiberg Bond Indices for 1, 2a, 2b, 3a and 6b across 

different basis sets (M1 = Mg or Zn, M2 = Pd or Pt) 

  1 3a 2a 2b 6b 

  BS1 BS3 BS4 BS1 BS3 BS4 BS1 BS4 BS1 BS4 BS1 BS2 

NPA 
charge 

M1 1.61 1.59 1.60 1.38 1.40 1.40 1.54 1.51 1.26 1.28 1.61–1.67 1.61–1.67 

M2 - - - - - - –0.23 –0.24 –0.16 –0.17 –0.56 –0.56 

H –0.72 –0.71 –0.71 –0.54 –0.56 –0.56 –0.51 –0.50 –0.41 –0.41 –0.52 - –0.58 –0.52 - –0.58 

WBI 

M1–M2 - - - - - - 0.23 0.24 0.31 0.30 0.11-0.17 0.11-0.17 

M1–H 0.43 0.45 0.45 0.61 0.59 0.59 0.21 0.23 0.31 0.29 0.10-0.11 0.09-0.11 

M2–H - - - - - - 0.39 0.37 0.37 0.36 0.30-0.37 0.30-0.37 

M1 = Mg (1, 2a, 6b), Zn (3a, 2b); M2 = Pd (2a, 2b), Pt (6b) 

 

 



S25 
 

Table S3. Comparison of selected bond lengths (Å) between computed model (4’, 5’ and 6b’ using 
BS3) and full (4, 5 and 6b using BS1 or BS2) systems. 

 4’  4  5’ 5 6b’ 6b 

M1–H 1.75 1.73, 1.74 1.75 1.77-1.81 2.24-2.26 2.18-2.43 

M2–H 1.68 1.68, 1.69 1.70 1.69, 1.71 1.68 1.69, 1.71 

M1–M2 2.46 2.45-2.48 2.54 2.48, 2.49 2.56 2.59, 2.61 

M1 = Zn (4’, 4, 5’ and 5), Mg (6b’ and 6b); M2 = Pd (4’, 4, 5’ and 5), Pt (6b’ and 6b) 

 

Table S4. Comparison of NPA charges and Wiberg Bond Indices between computed model (4’ using 
BS1; 5’ and 6b’ using BS3) and full (4 and 5 using BS1 and 6b using BS2) systems. 

 4’  4  5’ 5 6b’ 6b 

M1 1.34 1.34-1.35 1.39 1.39-1.43 1.66 1.61-1.67 

M2 –0.15 –0.15 –0.10 –0.26 –0.55 –0.56 

H –0.43 - –0.44 –0.43 - –0.44 –0.36 –0.46 - –0.50  –0.48 –0.52 - –0.58 

M1–M2 0.26 0.25-0.26 0.24 0.14-0.18 0.45 0.11-0.17 

M1–H 0.33-0.34 0.33-0.35 0.45 0.30-0.32 0.34 0.09-0.11 

M2–H 0.32-0.33 0.32-0.33 0.29 0.25-0.28 0.63, 0.64  0.30-0.37 

M1 = Zn (4’, 4, 5’ and 5), Mg (6b’ and 6b); M2 = Pd (4’, 4, 5’ and 5), Pt (6b’ and 6b) 

 

 

 

 

 

 

 

 

 

 

 

 

 



S26 
 

8.3. Molecular Orbital Analysis 

 

Analysis of 2a’ (model) 

 

Figure S13. Qualitative MO diagram (idealised to Cs symmetry) of a model of 2a constructed from 
interaction of a bent PdL2 fragment with a {MgH}+ unit. 

 

Table S5. Relevant contributions of atomic orbitals to the key bonding molecular orbitals of a model of 
2a (contributions from P and C atoms have been omitted for clarity). 

MO AO contributions (from 
NBO analysis) 

 AO contributions (from 
NBO analysis) 

LUMO Mg: s = 22%, p = 48%  

Pd: d = 9%, p = 3%, s = 2% 

H: s = 7% 

 Mg: s = 4% 

Pd: d = 29%, p = 5% 

H: s = 20% 

HOMO Mg: s = 38%, p = 2%  

Pd: d = 15%, p = 8%, s = 4% 

 Mg: s = 4%, p = 2%  

Pd: d = 54% 

H: s = 4% 

 



S27 
 

Table S6. Main donor-acceptor interactions from NBO second order perturbation analysis for 
complexes 2a and 2b. 

Complex 
Orbitals involved (donor 

→ acceptor) 
 

Energy of the interaction 
(kcal·mol-1) 

2a 
Pd d → σ* (Mg-H) 

σ (Mg-H) → Pd s 
 

28.5 

300.3 

2b 
Pd d → σ* (Zn-H) 

σ (Zn-H) → Pd s 
 

37.3 

262.2 

 

  



S28 
 

 

Analysis of 5’ (model)  

 

Figure S14. Qualitative MO diagram (idealised to C3h symmetry) of 5’ constructed from interaction of 
a Pd fragment with three {ZnH}+ units. 



S29 
 

 

 

Table S7. Relevant contributions of atomic orbitals to the key bonding molecular orbitals of 5’ 

MO AO contributions (from 
NBO analysis) 

 MO AO contributions (from NBO 
analysis) 

LUMO Zn: s = 57.2%, p = 1.4%  

Pd: d = 0%, p = 0%, s = 0% 

H: s = 19.7% 

 HOMO-5 Zn: s = 10.3%, p = 0.3%  

Pd: d = 49.7%, p = 0.1%, s = 0% 

H: s = 30.4% 

HOMO Zn: s = 0%, p = 0%  

Pd: d = 80.6%, p = 0%, s = 0.3% 

H: s = 0% 

 HOMO-6 Zn: s = 9.6%, p = 0.2%  

Pd: d = 49.8%, p = 0.1%, s = 0% 

H: s = 28.5% 

HOMO-1 Zn: s = 20.1%, p = 0.5%  

Pd: d = 38.0%, p = 0.1%, s = 0% 

H: s = 33.8% 

 HOMO-7 Zn: s = 13.8%, p = 0.3%  

Pd: d = 16.0%, p = 0.4%, s = 97.1% 

H: s = 40.9% 

HOMO-2 Zn: s = 17.4%, p = 0.4%  

Pd: d = 38.1%, p = 0.1%, s = 0% 

H: s = 34.6% 

   

 

 

 

Figure S15. (a) Walsh diagram and (b) snapshots at different values of θ for the key e’ set (HOMO-5 
and HOMO-6) of orbitals of a model of 5, showcasing the decrease in Zn–H interactions upon 

extension. 



S30 
 

8.4. Symmetry Elements for the Hexagonal Planar Geometry 

 

Figure S16. Symmetry elements for 6a and 6b (D3h symmetry). 

 

  



S31 
 

8.5. PES for Hexagonal and Trigonal Planar Geometries 

 

 

Figure S17. Energy change upon systematic elongation of each Zn---H distance in PdZn3H3 model. 
Global minimum and maximum points are highlighted. This is a 1D representation of the 4D PES 

presented in the paper. 

 

 

Figure S18. Energy change upon symmetric compression of the Mg---H distances in 6a. This 

compression is plotted in terms of the angle  described in the paper and Figure 1. The red dot shows 

the calculated lowest energy  value for 6a. 

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

0 200 400 600 800 1000 1200 1400

E 
(k

ca
l･

m
o

l-1
)

Calculation Step Number

0

10

20

30

40

50

60

70

80

90

100

2530354045505560

E 
(k

ca
l･

m
o

l-1
)

θ (deg.)

Zn---H = 1.712 Å, 2.253 Å, 2.253 Å 

Zn---H = 1.766 Å, 1.767 Å, 1.767 Å 

systematic elongation of each Zn---H distance 



S32 
 

 

Figure S19. Energy change upon symmetric compression and elongation away from the optimised 

Zn–H distances in 5. This change is plotted in terms of the angle  described in the paper and Figure 

1. The red dot shows the calculated lowest energy  value for 5. 

 

 

The trends observed in the 4D PES for both the PtMg3H3 and PdZn3H3 model systems 

calculated at the BS3 level of theory remain consistent when calculated using a much smaller 

basis set (H: 6-31G; Mg, Zn, Pd, Pt: SDDAll). The largest calculated energy differences using 

either level of theory are similar (PtMg3H3: +19.4 kcal mol-1 (low) and +14.6 kcal mol-1 (BS3); 

PdZn3H3: +5.5 kcal mol-1 (low) and +4.6 kcal mol-1 (BS3)). The 4D PES for both are presented 

below. 

 

Figure S20. Potential energy surface for PtMg3H3 (left) and PdZn3H3 (right) model systems calculated 
using small basis sets (scale in kcal mol-1). 

  



S33 
 

8.6. Vibrational analysis for Hexagonal and Trigonal Planar 

Geometries 

 

 

Figure S21. Computed vibrational modes for models 5’ and 6b’ including associated wavenumbers 
for both hydride and deuteride analogues 

 

The computed stretching frequencies of various vibrational modes for simplified models 5’ and 

6b’ were analysed. The models, consisting of only metals and metal hydrides ({PdZn3H3}3+, 5’ 

and {PtMg3H3}3+, 6b’) were calculated at the BS3 level of theory (see computational methods). 

Frequency calculations revealed 15 vibrational modes in each case. The symmetric and 

asymmetric M---H stretches (M = Pd or Zn (5’) and Pt or Mg (6b’)) are presented in Figure 

S21 along with their calculated wavenumbers for both metal hydrides and deuterides.  

 

Assuming a highly simplified harmonic oscillator, the stretching frequencies can be 

rationalised by considering the reduced mass of the bond which is vibrating. A comparison of 



S34 
 

the calculated wavenumbers for each M---H mode against the corresponding M---D mode are 

in good agreement (0.2 – 0.6%) with the approximation below: 

𝜈2 = √
𝜈1
2𝜇1

𝜇2
      (eq. 1) 

where 1 and 1 are the computed wavenumber and reduced mass of the reference 

vibration, respectively, and 2 is the wavenumber to be calculated. 

 

The much lower computed wavenumbers for the Mg–H and Mg–D stretch relative to Zn–H 

and Zn–D stretch cannot be accounted for by differences in reduced mass alone. Rather the 

computed values are consistent with considerably weaker interaction, and smaller force 

constant, in Mg---H than in Zn---H.  

 

To unequivocally confirm the signal at 1705 cm-1 to be the terminal Pt–H stretch in 6b, the 

deuterium isotopologue (d3-6b) was prepared, confirming disappearance of this signal by both 

1H NMR and IR spectroscopies. Based on computed Pt–H stretches, the experimentally 

observed Pt–D stretch would be expected to be around 1201 cm-1, within the fingerprint region 

of the spectrum. Unfortunately, no definitive Pt–D stretch could be identified due to 

overlapping peaks and likely broadening. 

    

Figure S22. Comparison of infrared (left) and 1H NMR (right) spectra of 6b and d3-6b  

5001000150020002500300035004000

30

40

50

60

70

80

90

100

T
ra

n
s
m

it
ta

n
c
e

 (
%

)

Wavenumber (cm-1)

 6b

 d3-6b

-10.5-10.0-9.5-9.0-8.5-8.0-7.5-7.0-6.5-6.0-5.5-5.0-4.5-4.0
δ/ppm

6b 

d3-6b 



S35 
 

9. XYZ Coordinates 

1 
 
SCF (wB97x) =   -1240.51583393 
E(SCF)+ZPE(0 K)=   -1239.862364 
H(298 K)=   -1239.825287 
G(298 K)=   -1239.932430 
Lowest Frequency = 9.8772cm-1 
 
N        9.078906    4.681070    3.180555 
C        7.869377    5.047131    2.773845 
C        7.231752    6.245049    3.150072 
H        6.247169    6.402326    2.724647 
C        7.677528    7.248434    4.031716 
N        8.854986    7.239387    4.644867 
C        7.095901    4.129016    1.851663 
H        7.665040    3.933949    0.935905 
H        6.129138    4.558144    1.581824 
H        6.929214    3.157744    2.331291 
C        6.725119    8.396803    4.288168 
H        6.465520    8.447850    5.351754 
H        5.807132    8.289923    3.707249 
H        7.196610    9.352493    4.033320 
C        9.612231    3.414058    2.772619 
C       10.409643    3.332349    1.614986 
C       10.996412    2.107513    1.294252 
H       11.621519    2.030263    0.407170 
C       10.804103    0.987348    2.091463 
H       11.272163    0.042309    1.827899 
C       10.015633    1.081721    3.230581 
H        9.874595    0.202890    3.856140 
C        9.409039    2.285392    3.590898 
C       10.677009    4.551739    0.743526 
H        9.972236    5.337293    1.038316 
C       12.096071    5.084703    0.986576 
H       12.267419    5.315695    2.045685 
H       12.275687    5.995134    0.402132 
H       12.845568    4.339843    0.692447 
C       10.449974    4.272558   -0.746299 
H       10.563415    5.195401   -1.326569 
H        9.445434    3.874928   -0.931723 
H       11.173277    3.548351   -1.138745 
C        8.589130    2.369439    4.871557 
H        8.028217    3.310556    4.851693 
C        7.566991    1.234373    4.995148 
H        6.912829    1.187482    4.116925 
H        6.938520    1.384913    5.880373 
H        8.053695    0.257995    5.102030 
C        9.512026    2.405172    6.097959 
H       10.082831    1.472266    6.181239 
H        8.932031    2.532346    7.020311 
H       10.241132    3.223533    6.035925 
C        9.185774    8.289458    5.563625 

C        8.888862    8.126885    6.931295 
C        9.303812    9.113285    7.826333 
H        9.088800    8.998845    8.886605 
C        9.994882   10.235568    7.388864 
H       10.313982   10.992475    8.100831 
C       10.281341   10.382899    6.038559 
H       10.829968   11.260077    5.701948 
C        9.886051    9.422169    5.106669 
C        8.175718    6.883824    7.446672 
H        7.739183    6.364490    6.586189 
C        7.028584    7.214566    8.407406 
H        7.393524    7.665095    9.337704 
H        6.485508    6.301735    8.677645 
H        6.315986    7.913495    7.954514 
C        9.177597    5.926009    8.106887 
H        9.998615    5.662528    7.427409 
H        8.683079    4.998993    8.422131 
H        9.630050    6.388245    8.992709 
C       10.254151    9.594267    3.639493 
H        9.690804    8.852591    3.062152 
C       11.748295    9.315425    3.423607 
H       12.361481   10.042260    3.970240 
H       12.007747    9.385282    2.360347 
H       12.031163    8.317672    3.782554 
C        9.875778   10.976751    3.096537 
H        8.813599   11.194421    3.257811 
H       10.074402   11.028931    2.019932 
H       10.456217   11.773798    3.575604 
Mg       10.264761    5.798818    4.394334 
H       11.862192    5.603861    4.978838 
  
2a 
 
SCF (wB97x) =   -3270.13166716 
E(SCF)+ZPE(0 K)=   -3268.758409 
H(298 K)=   -3268.689251 
G(298 K)=   -3268.864927 
Lowest Frequency = 7.7918cm-1 
 
Pd        0.933721   -0.408713   -0.112826 
Mg       -1.339837    0.184827   -1.095783 
H        0.377115   -0.445706   -1.715654 
N       -2.009037    1.981241   -1.875453 
C       -2.965126    2.046578   -2.783479 
C       -3.806793    0.961866   -3.121662 
H       -4.519759    1.161627   -3.915374 
C       -3.942696   -0.281804   -2.479750 
N       -3.141498   -0.724182   -1.515635 
C       -3.218941    3.323249   -3.563813 
H       -2.726355    4.190548   -3.120035 
H       -4.292210    3.521142   -3.640514 
H       -2.835622    3.198109   -4.583793 



S36 
 

C       -5.117285   -1.134821   -2.915763 
H       -4.805757   -2.167813   -3.100576 
H       -5.580321   -0.734778   -3.820198 
H       -5.877506   -1.168827   -2.126198 
C       -1.295025    3.144178   -1.450530 
C       -1.796167    3.888753   -0.360494 
C       -1.053556    4.973879    0.106670 
H       -1.435215    5.567625    0.934838 
C        0.166876    5.311079   -0.465025 
H        0.732875    6.158969   -0.086435 
C        0.653973    4.563209   -1.528358 
H        1.606623    4.834294   -1.979674 
C       -0.059249    3.477288   -2.041312 
C       -3.141896    3.562598    0.277140 
H       -3.443980    2.567218   -0.069802 
C       -3.076187    3.512416    1.806721 
H       -2.342049    2.772911    2.148695 
H       -4.053184    3.235338    2.219460 
H       -2.804398    4.483383    2.237960 
C       -4.215393    4.560831   -0.177822 
H       -3.961084    5.578552    0.144021 
H       -5.191081    4.303753    0.251723 
H       -4.317003    4.571843   -1.268423 
C        0.495118    2.724438   -3.243197 
H       -0.144550    1.852427   -3.419392 
C        0.451085    3.602916   -4.501346 
H       -0.561678    3.969386   -4.702930 
H        0.791378    3.038069   -5.377316 
H        1.104491    4.477482   -4.391573 
C        1.915755    2.204012   -2.998310 
H        2.624704    3.027433   -2.839995 
H        2.261572    1.628617   -3.866268 
H        1.938648    1.541789   -2.125765 
C       -3.485341   -1.916845   -0.805248 
C       -2.857845   -3.138113   -1.123312 
C       -3.158091   -4.266545   -0.356067 
H       -2.684311   -5.215864   -0.599615 
C       -4.048276   -4.202103    0.706401 
H       -4.267510   -5.090888    1.293363 
C       -4.658561   -2.992115    1.013997 
H       -5.355867   -2.944429    1.847994 
C       -4.397573   -1.841170    0.270377 
C       -1.878150   -3.272218   -2.280943 
H       -1.761211   -2.284893   -2.741467 
C       -2.410566   -4.224855   -3.359262 
H       -2.530617   -5.242295   -2.967341 
H       -1.714281   -4.272580   -4.204680 
H       -3.384807   -3.898507   -3.741212 
C       -0.494562   -3.719353   -1.794456 
H       -0.098019   -3.015214   -1.053095 
H        0.212659   -3.752060   -2.633317 
H       -0.531689   -4.720134   -1.344308 
C       -5.073910   -0.530376    0.653253 
H       -4.960139    0.169927   -0.180962 
C       -4.382542    0.099044    1.868534 

H       -4.412692   -0.578837    2.731598 
H       -4.875940    1.036067    2.154311 
H       -3.329030    0.320563    1.656119 
C       -6.576195   -0.693267    0.911852 
H       -7.077967   -1.184045    0.069852 
H       -7.042113    0.287533    1.061199 
H       -6.774660   -1.288490    1.810905 
P        3.293614   -0.905044   -0.064058 
C        3.679022   -1.177254    1.741975 
H        3.560071   -2.252846    1.913689 
H        4.730613   -0.950696    1.960717 
C        2.769009   -0.398809    2.709615 
H        3.137358    0.630441    2.795815 
H        2.838780   -0.834308    3.715575 
P        0.970775   -0.259221    2.187516 
C        4.465145    0.449548   -0.581798 
H        4.247627    0.585521   -1.653333 
C        4.104262    1.772293    0.114614 
H        3.034529    1.985742   -0.008416 
H        4.287658    1.674750    1.196344 
C        4.945403    2.934311   -0.419776 
H        4.699457    3.096082   -1.479970 
H        4.683324    3.859107    0.109567 
C        6.442113    2.646784   -0.284807 
H        6.703451    2.589150    0.782551 
H        7.030509    3.469906   -0.708523 
C        6.811432    1.326488   -0.963836 
H        7.877401    1.108838   -0.822173 
H        6.650496    1.420576   -2.048073 
C        5.966295    0.161649   -0.434547 
H        6.241059   -0.759055   -0.963915 
H        6.208681   -0.001467    0.626478 
C        4.020283   -2.429145   -0.847464 
H        5.038304   -2.588778   -0.456536 
C        4.097241   -2.256397   -2.374254 
H        4.745744   -1.410759   -2.635954 
H        3.092372   -2.009681   -2.749654 
C        4.610125   -3.521312   -3.069605 
H        4.621414   -3.367230   -4.155698 
H        5.652110   -3.704110   -2.766415 
C        3.762180   -4.742414   -2.712350 
H        2.743708   -4.603307   -3.104606 
H        4.166525   -5.642529   -3.191641 
C        3.692917   -4.928644   -1.196335 
H        4.696476   -5.167948   -0.813588 
H        3.048147   -5.779998   -0.944761 
C        3.171025   -3.665729   -0.505049 
H        3.140289   -3.830229    0.579721 
H        2.135175   -3.478872   -0.821633 
C        0.177933   -1.631284    3.164483 
H        0.475842   -1.509471    4.217864 
C        0.686732   -3.002616    2.690727 
H        0.466263   -3.114105    1.617825 
H        1.777216   -3.062978    2.799520 
C        0.036214   -4.147387    3.473145 



S37 
 

H        0.400923   -5.109810    3.092474 
H        0.346560   -4.087024    4.527365 
C       -1.488955   -4.084645    3.388656 
H       -1.937632   -4.891279    3.982300 
H       -1.801294   -4.242177    2.346499 
C       -2.008514   -2.725749    3.859736 
H       -3.098295   -2.675896    3.736454 
H       -1.802343   -2.606729    4.934350 
C       -1.354904   -1.578623    3.083229 
H       -1.727942   -0.617668    3.462643 
H       -1.658184   -1.641217    2.027331 
C        0.454476    1.286691    3.097780 
H       -0.640789    1.315474    2.983461 
C        0.776448    1.303495    4.600621 
H        1.861275    1.193847    4.746930 
H        0.302876    0.451322    5.104145 
C        0.322579    2.606623    5.266521 
H       -0.774280    2.676790    5.214240 
H        0.587236    2.591141    6.331186 
C        0.936816    3.824789    4.576533 
H        2.030528    3.794729    4.695489 
H        0.592935    4.749523    5.056252 
C        0.585110    3.833230    3.088713 
H        1.050645    4.688692    2.583277 
H       -0.500505    3.960696    2.977645 
C        1.014376    2.537005    2.394624 
H        2.114476    2.496037    2.386946 
H        0.694671    2.546112    1.343574 
  
2b 
 
SCF (wB97x) =   -4849.50272730 
E(SCF)+ZPE(0 K)=   -4848.128772 
H(298 K)=   -4848.059609 
G(298 K)=   -4848.233962 
Lowest Frequency = 9.1108cm-1 
 
Pd       -0.858395    0.448530   -0.051956 
Zn        1.265121   -0.255873   -1.047217 
H       -0.322086    0.432664   -1.634931 
N        1.739548   -2.073913   -1.845186 
C        2.687918   -2.223724   -2.747431 
C        3.619830   -1.216858   -3.084037 
H        4.319625   -1.475967   -3.872096 
C        3.848413    0.008249   -2.439575 
N        3.078888    0.512541   -1.481020 
C        2.833704   -3.519528   -3.523956 
H        2.247809   -4.335047   -3.096049 
H        3.884465   -3.820796   -3.572633 
H        2.492421   -3.356185   -4.553396 
C        5.087498    0.770128   -2.865966 
H        4.853583    1.820641   -3.066117 
H        5.530310    0.327238   -3.760626 
H        5.838655    0.758222   -2.067409 
C        0.915470   -3.159995   -1.423796 

C        1.329486   -3.939056   -0.322497 
C        0.474424   -4.936345    0.148626 
H        0.784252   -5.555554    0.988085 
C       -0.768361   -5.153899   -0.433571 
H       -1.423206   -5.932937   -0.050133 
C       -1.161078   -4.381294   -1.518709 
H       -2.128129   -4.565578   -1.983726 
C       -0.333363   -3.382565   -2.036582 
C        2.702168   -3.751091    0.313054 
H        3.099678   -2.788802   -0.029543 
C        2.651673   -3.704308    1.842481 
H        1.995966   -2.898323    2.192034 
H        3.654014   -3.525907    2.248917 
H        2.290874   -4.647606    2.269997 
C        3.667994   -4.850244   -0.151537 
H        3.313167   -5.838389    0.167553 
H        4.666240   -4.694814    0.274973 
H        3.763969   -4.867354   -1.242445 
C       -0.774861   -2.607070   -3.270134 
H       -0.038803   -1.815952   -3.449561 
C       -0.802531   -3.520377   -4.503808 
H        0.166535   -4.003384   -4.671357 
H       -1.058651   -2.946472   -5.402343 
H       -1.552169   -4.313081   -4.387289 
C       -2.133208   -1.926817   -3.075115 
H       -2.933020   -2.662220   -2.916626 
H       -2.394028   -1.338468   -3.964069 
H       -2.099879   -1.248083   -2.216500 
C        3.512530    1.671283   -0.766610 
C        3.001688    2.940455   -1.100092 
C        3.392109    4.042519   -0.335707 
H        3.006757    5.028766   -0.588705 
C        4.263702    3.905013    0.735743 
H        4.555927    4.774222    1.320356 
C        4.763523    2.647907    1.053975 
H        5.449446    2.544384    1.892345 
C        4.407159    1.519792    0.314572 
C        2.049451    3.145461   -2.268881 
H        1.883077    2.171130   -2.740535 
C        2.645213    4.082015   -3.327618 
H        2.810734    5.088352   -2.923847 
H        1.964819    4.174111   -4.182336 
H        3.607261    3.710848   -3.699645 
C        0.688839    3.660462   -1.787168 
H        0.252782    2.965991   -1.059304 
H       -0.009375    3.746879   -2.630155 
H        0.777678    4.649823   -1.318769 
C        4.966511    0.156449    0.701979 
H        4.806633   -0.528844   -0.137041 
C        4.206866   -0.417882    1.903376 
H        4.284717    0.250677    2.770909 
H        4.615412   -1.394880    2.189332 
H        3.142048   -0.545910    1.672294 
C        6.473230    0.192544    0.981962 
H        7.026496    0.643565    0.149942 



S38 
 

H        6.853182   -0.824566    1.132051 
H        6.707921    0.764346    1.887513 
P       -3.164359    1.098306   -0.041997 
C       -3.576138    1.436761    1.745248 
H       -3.389791    2.505597    1.896023 
H       -4.645724    1.285765    1.938926 
C       -2.743924    0.623642    2.751841 
H       -3.184863   -0.374388    2.858638 
H       -2.800398    1.091195    3.743949 
P       -0.952944    0.351969    2.268461 
C       -4.396480   -0.202141   -0.558784 
H       -4.182381   -0.355248   -1.628033 
C       -4.105217   -1.536957    0.147098 
H       -3.048826   -1.808500    0.022050 
H       -4.278839   -1.421391    1.228563 
C       -5.008342   -2.657910   -0.373807 
H       -4.771434   -2.846508   -1.431515 
H       -4.795503   -3.588509    0.167294 
C       -6.487426   -2.288774   -0.245481 
H       -6.747176   -2.201624    0.820271 
H       -7.118678   -3.084883   -0.658914 
C       -6.783086   -0.960547   -0.944503 
H       -7.836786   -0.684888   -0.812757 
H       -6.620775   -1.077588   -2.026289 
C       -5.881457    0.165172   -0.424133 
H       -6.104554    1.091757   -0.967471 
H       -6.122924    0.353632    0.632759 
C       -3.793303    2.639236   -0.875331 
H       -4.813025    2.848089   -0.513465 
C       -3.841543    2.440470   -2.399954 
H       -4.519587    1.618151   -2.661240 
H       -2.839917    2.144343   -2.747121 
C       -4.283908    3.712151   -3.130431 
H       -4.275206    3.537879   -4.213441 
H       -5.324410    3.943536   -2.856840 
C       -3.394534    4.903481   -2.773771 
H       -2.373373    4.714989   -3.137282 
H       -3.748777    5.810231   -3.279357 
C       -3.355663    5.115793   -1.260139 
H       -4.357773    5.403392   -0.908066 
H       -2.682708    5.944595   -1.007397 
C       -2.904073    3.846625   -0.531546 
H       -2.897232    4.031548    0.550222 
H       -1.868700    3.613463   -0.814564 
C       -0.085097    1.694604    3.218410 
H       -0.391039    1.610423    4.273220 
C       -0.511117    3.084852    2.718865 
H       -0.282350    3.165240    1.644901 
H       -1.596018    3.212812    2.824835 
C        0.206144    4.201009    3.484107 
H       -0.100386    5.177317    3.087874 
H       -0.108129    4.175652    4.538613 
C        1.724837    4.045952    3.402439 
H        2.220462    4.833950    3.983647 
H        2.045471    4.167914    2.358223 

C        2.162794    2.666254    3.895468 
H        3.247394    2.549209    3.772825 
H        1.951210    2.577618    4.972035 
C        1.441369    1.547247    3.138437 
H        1.754187    0.572615    3.536384 
H        1.746929    1.568825    2.081767 
C       -0.553070   -1.202563    3.217986 
H        0.538295   -1.310621    3.116429 
C       -0.892179   -1.157978    4.716707 
H       -1.965998   -0.956896    4.846711 
H       -0.355907   -0.335536    5.206542 
C       -0.555484   -2.477615    5.418525 
H        0.532257   -2.639360    5.383744 
H       -0.831317   -2.414327    6.478543 
C       -1.259945   -3.657158    4.747832 
H       -2.348966   -3.532430    4.846749 
H       -1.002567   -4.594897    5.255588 
C       -0.885666   -3.732214    3.267497 
H       -1.411592   -4.558957    2.773367 
H        0.187346   -3.950464    3.182199 
C       -1.196153   -2.423660    2.534489 
H       -2.289187   -2.297939    2.503471 
H       -0.858818   -2.483958    1.490947 
  
3a 
 
SCF (wB97x) =   -1466.79656213 
E(SCF)+ZPE(0 K)=   -1466.142298 
H(298 K)=   -1466.105165 
G(298 K)=   -1466.212380 
Lowest Frequency = 9.4843cm-1 
 
N        9.022172    4.655857    3.244742 
C        7.813302    5.013857    2.831759 
C        7.162972    6.198263    3.221242 
H        6.176755    6.353453    2.799158 
C        7.621903    7.207893    4.085774 
N        8.800566    7.190273    4.694577 
C        7.067199    4.104515    1.880046 
H        7.642197    3.956463    0.959068 
H        6.090148    4.518050    1.622921 
H        6.925693    3.113782    2.326370 
C        6.694588    8.379866    4.322379 
H        6.455415    8.472130    5.387781 
H        5.765040    8.267557    3.761067 
H        7.176521    9.317908    4.024802 
C        9.602820    3.426763    2.790466 
C       10.415277    3.430518    1.641155 
C       11.044490    2.241929    1.269225 
H       11.682582    2.226873    0.388452 
C       10.876968    1.078597    2.008709 
H       11.377989    0.162626    1.705800 
C       10.069808    1.090685    3.138469 
H        9.947286    0.177333    3.716399 
C        9.420326    2.255464    3.549096 



S39 
 

C       10.653210    4.704617    0.842138 
H        9.882883    5.429835    1.126797 
C       12.015054    5.314474    1.202217 
H       12.097401    5.505387    2.279225 
H       12.170074    6.262187    0.672119 
H       12.829172    4.632837    0.926452 
C       10.537140    4.487786   -0.670273 
H       10.612225    5.446534   -1.195957 
H        9.579315    4.026476   -0.937559 
H       11.337226    3.843363   -1.052704 
C        8.579114    2.255048    4.818169 
H        7.966037    3.163066    4.816154 
C        7.622872    1.060262    4.895818 
H        6.990243    0.993590    4.003053 
H        6.969254    1.155827    5.770373 
H        8.162808    0.111401    4.994930 
C        9.482288    2.312179    6.057980 
H       10.114333    1.417529    6.117874 
H        8.882539    2.367354    6.974745 
H       10.148108    3.183402    6.029534 
C        9.178919    8.267758    5.560648 
C        8.896273    8.178858    6.936565 
C        9.354289    9.195569    7.775340 
H        9.152412    9.140583    8.842762 
C       10.070807   10.273429    7.272396 
H       10.422808   11.054575    7.941508 
C       10.338810   10.348032    5.911988 
H       10.905262   11.192332    5.525393 
C        9.901092    9.355240    5.034577 
C        8.154521    6.983195    7.518368 
H        7.662874    6.457271    6.692498 
C        7.062596    7.388845    8.513869 
H        7.483638    7.840956    9.419423 
H        6.489965    6.507976    8.825878 
H        6.365011    8.110382    8.072920 
C        9.143922    6.003276    8.164130 
H        9.911456    5.679108    7.450694 
H        8.623157    5.112864    8.537184 
H        9.659792    6.475326    9.009415 
C       10.248574    9.435059    3.554314 
H        9.604590    8.728975    3.018512 
C       11.702125    8.999600    3.322438 
H       12.395863    9.682207    3.828644 
H       11.943288    9.000731    2.252369 
H       11.887090    7.992454    3.715624 
C        9.995191   10.823966    2.958810 
H        8.967386   11.158155    3.142119 
H       10.159715   10.805943    1.875396 
H       10.671942   11.577435    3.378297 
Zn       10.111151    5.734094    4.483355 
H       11.506293    5.513594    5.080859 
 
3b 
 
SCF (wB97x) =   -1230.98337177 

E(SCF)+ZPE(0 K)=   -1230.504485 
H(298 K)=   -1230.474150 
G(298 K)=   -1230.567836 
Lowest Frequency = 11.3898cm-1 
 
N        9.057938    4.649278    3.258462 
C        7.848816    5.007427    2.844882 
C        7.197209    6.191120    3.233818 
H        6.211048    6.345260    2.811182 
C        7.654409    7.201063    4.098649 
N        8.833165    7.186049    4.708255 
C        7.101669    4.098441    1.891764 
H        7.674393    3.949236    0.970062 
H        6.125511    4.514455    1.635044 
H        6.956494    3.107598    2.335632 
C        6.722823    8.371376    4.334176 
H        6.480135    8.464748    5.398259 
H        5.794583    8.254864    3.771463 
H        7.199490    9.311638    4.036707 
C        9.630613    3.421237    2.801481 
C       10.435559    3.416600    1.653495 
C       11.018205    2.216670    1.248430 
H       11.638593    2.209854    0.352742 
C       10.834531    1.032587    1.960016 
C       10.044194    1.070981    3.107265 
H        9.893958    0.157674    3.682162 
C        9.443023    2.249065    3.547667 
C        9.201050    8.265821    5.570575 
C        8.915995    8.186194    6.941094 
C        9.319754    9.230735    7.771269 
H        9.093174    9.173740    8.835515 
C       10.008791   10.337559    7.278902 
C       10.294225   10.381053    5.915511 
H       10.838579   11.234104    5.511550 
C        9.908978    9.358410    5.050013 
Zn       10.144710    5.730403    4.496889 
H       11.539369    5.512384    5.094353 
C        8.200191    6.985040    7.504879 
H        7.223310    6.828162    7.032308 
H        8.781147    6.068610    7.340593 
H        8.042446    7.095762    8.581951 
C       10.258299    9.415221    3.584499 
H       10.898824    8.570698    3.300273 
H        9.368026    9.364573    2.946421 
H       10.793741   10.339486    3.347311 
C       10.465057   11.440143    8.201987 
H        9.789008   11.550466    9.056209 
H       11.465711   11.230994    8.599507 
H       10.513249   12.402044    7.681090 
C       10.676671    4.690089    0.883376 
H       11.178027    5.438937    1.509619 
H       11.308589    4.503277    0.009870 
H        9.741441    5.144737    0.535684 
C        8.619242    2.269717    4.810191 
H        9.059477    2.944241    5.555551 



S40 
 

H        7.597138    2.623166    4.629649 
H        8.559818    1.270830    5.252825 
C       11.502342   -0.247104    1.521426 
H       11.641511   -0.272578    0.435666 
H       12.492110   -0.351894    1.982356 
H       10.912209   -1.123638    1.808417 
  
4 
 
SCF (wB97x) =   -12680.5777333 
E(SCF)+ZPE(0 K)=   -12677.717906 
H(298 K)=   -12677.555552 
G(298 K)=   -12677.924919 
Lowest Frequency = 4.9080cm-1 
 
Pd       -6.349774    6.315665    9.479015 
Zn       -8.356696    4.908909    9.463290 
Zn       -6.924260    7.567717    7.445596 
N       -7.431317    7.571463    5.511933 
N       -7.153170    9.562652    7.694871 
C       -7.821214   10.305853    6.827296 
C       -8.276525    9.843397    5.577134 
H       -8.797620   10.576711    4.971708 
C       -7.021236    6.474003    4.686614 
C       -7.858791    5.349364    4.543922 
C       -8.258452    8.617038    3.437550 
H       -8.531191    7.628600    3.064346 
H       -9.050609    9.328176    3.189983 
H       -7.353109    8.926843    2.900721 
C       -5.770530    6.530407    4.038648 
C       -6.534195   10.182139    8.828357 
C       -6.225607    4.369265    3.036472 
C       -8.111568   11.759100    7.144819 
H       -7.212481   12.280672    7.485888 
H       -8.513237   12.278758    6.272367 
H       -8.846593   11.824311    7.954339 
C       -5.393757    5.465638    3.218381 
H       -4.430906    5.495479    2.712476 
C       -7.444205    4.316028    3.701078 
H       -8.088380    3.451007    3.561001 
C       -7.260710   10.415176   10.011261 
C       -5.158421   10.505275    8.749053 
C       -4.551984   11.104416    9.854440 
H       -3.498572   11.369869    9.814836 
C       -6.604521   11.007409   11.093855 
H       -7.156257   11.192575   12.013947 
C       -5.265822   11.360992   11.020242 
C       -7.981716    8.630997    4.929339 
H       -5.479911    6.909715    8.168794 
H       -7.357382    5.680179   10.666936 
N       -8.015974    2.919481    9.281851 
N      -10.338240    4.770390    9.580064 
C      -10.976642    3.632689    9.305732 
C      -10.356987    2.422754    8.958723 
H      -11.030940    1.606767    8.721298 

C       -8.993043    2.063477    9.049425 
C      -12.490573    3.602672    9.382366 
H      -12.875282    2.610348    9.139411 
H      -12.834873    3.876758   10.385083 
H      -12.929020    4.328393    8.689589 
C       -8.705976    0.578982    8.939387 
H       -8.788225    0.112328    9.928407 
H       -9.439524    0.099346    8.285720 
H       -7.701023    0.377839    8.562561 
C       -6.707899    2.442465    9.620018 
C       -6.461634    1.957269   10.921080 
C       -5.662080    2.532065    8.677851 
C       -5.171598    1.531704   11.245679 
C       -4.392210    2.085001    9.046953 
C       -4.141755    1.583126   10.317717 
H       -4.970690    1.154100   12.246342 
H       -3.580961    2.132173    8.325104 
C      -11.087720    5.854731   10.149114 
C      -11.724640    6.806077    9.327254 
C      -11.161176    5.967281   11.554421 
C      -12.463750    7.827558    9.928456 
C      -11.939019    6.985660   12.107952 
C      -12.594194    7.911017   11.307492 
H      -12.957974    8.566252    9.300622 
H      -12.021781    7.063725   13.190105 
N       -4.585422    6.547147   11.045769 
C       -3.520467    7.358787   10.454173 
H       -3.198631    6.897179    9.514510 
H       -3.913169    8.356685   10.232761 
H       -2.648473    7.449975   11.118608 
C       -4.089163    5.206965   11.366576 
H       -4.885286    4.621604   11.837311 
H       -3.806490    4.696715   10.439682 
H       -3.211152    5.229427   12.033354 
C       -5.196460    7.221662   12.205095 
H       -5.681415    8.128251   11.822621 
H       -5.992498    6.561807   12.566828 
C       -4.347987   10.209951    7.488628 
H       -4.719922    9.260281    7.083201 
C       -8.716877   10.004249   10.170536 
H       -9.081173    9.655104    9.198289 
C       -9.210078    5.264001    5.242551 
H       -9.186986    5.967078    6.082994 
C       -4.808451    7.695289    4.235589 
H       -5.341769    8.496559    4.759304 
C      -11.621314    6.777235    7.809278 
H      -11.120349    5.845236    7.523454 
C      -10.411917    5.030561   12.494451 
H       -9.774515    4.377389   11.888256 
C       -5.903594    3.056599    7.270558 
H       -6.741252    3.760926    7.324200 
C       -7.535401    1.924759   12.001843 
H       -8.502420    2.152889   11.540733 
C       -4.239559    7.592089   13.353113 
H       -3.549745    8.380665   13.030664 



S41 
 

H       -3.622561    6.732445   13.643205 
N       -4.905562    8.078202   14.576657 
C       -5.737335    9.256970   14.323850 
H       -6.630055    9.017743   13.721145 
H       -6.070304    9.673107   15.280068 
H       -5.148113   10.013964   13.795941 
C       -5.706457    7.041510   15.229773 
H       -5.078406    6.169070   15.438004 
H       -6.082780    7.432892   16.179456 
H       -6.572441    6.725639   14.623210 
Pd       -3.168399    8.812616   16.075843 
Zn       -3.057798    8.693652   18.546421 
Zn       -1.121196   10.156036   15.795812 
N       -0.182163   11.867802   16.228223 
N        0.455159    9.304984   14.850537 
C        1.676342    9.802542   14.938391 
C        1.996982   11.009578   15.594789 
H        3.050302   11.267540   15.593962 
C       -0.955528   13.032583   16.551753 
C       -1.151059   13.421944   17.892415 
C        1.786315   13.325627   16.434429 
H        1.637964   13.563328   17.492184 
H        2.858247   13.299441   16.229755 
H        1.339706   14.144944   15.861553 
C       -1.533557   13.777695   15.502048 
C        0.210212    8.228480   13.938200 
C       -2.447918   15.328779   17.129598 
C        2.835499    9.121236   14.236948 
H        2.907554    9.480540   13.203239 
H        3.776100    9.362433   14.738892 
H        2.715728    8.036506   14.197510 
C       -2.257914   14.929485   15.813751 
H       -2.690736   15.520476   15.008964 
C       -1.907645   14.566087   18.155802 
H       -2.064555   14.872949   19.188222 
C        0.011869    6.922604   14.428018 
C        0.132366    8.499400   12.555477 
C       -0.083393    7.436511   11.677740 
H       -0.134232    7.628429   10.607693 
C       -0.211490    5.893510   13.509901 
H       -0.350291    4.877779   13.871387 
C       -0.246842    6.138721   12.143880 
C        1.134079   12.003771   16.080179 
H       -2.660891   10.001235   14.991422 
H       -3.503682    7.646288   17.240893 
N       -4.600240    9.549382   19.542483 
N       -2.022217    8.225483   20.195601 
C       -2.329410    8.736833   21.386176 
C       -3.423939    9.576711   21.648146 
H       -3.497437    9.939906   22.666791 
C       -4.524447    9.875356   20.821035 
C       -1.465425    8.402989   22.587367 
H       -1.921555    8.772763   23.507717 
H       -1.310789    7.323881   22.679838 
H       -0.475808    8.859835   22.485464 

C       -5.697224   10.558419   21.493037 
H       -6.541153    9.864988   21.580280 
H       -5.429095   10.902091   22.494295 
H       -6.047480   11.410633   20.904204 
C       -5.859161    9.663043   18.867289 
C       -6.755367    8.573683   18.920929 
C       -6.177150   10.817686   18.125806 
C       -7.956942    8.658332   18.215421 
C       -7.398011   10.860112   17.448010 
C       -8.283839    9.791813   17.482248 
H       -8.654106    7.822924   18.247306 
H       -7.656851   11.750838   16.878398 
C       -0.997311    7.222390   20.138295 
C        0.364135    7.577358   20.078515 
C       -1.387337    5.863369   20.141208 
C        1.321423    6.559578   20.084457 
C       -0.392943    4.884700   20.159299 
C        0.954485    5.223748   20.142513 
H        2.376730    6.822386   20.044357 
H       -0.673379    3.835243   20.176393 
C        0.221341    9.914592   11.996117 
H        0.602840   10.576758   12.780662 
C        0.096192    6.610344   15.914135 
H       -0.165560    7.523643   16.458843 
C       -0.571430   12.643300   19.065022 
H        0.068625   11.852139   18.660206 
C       -1.398478   13.372051   14.039618 
H       -0.870666   12.412699   13.998610 
C        0.834140    9.022612   19.985768 
H       -0.035756    9.670838   20.135005 
C       -2.858422    5.457615   20.131857 
H       -3.404529    6.224781   19.569572 
C       -5.241444   12.014204   18.034963 
H       -4.342300   11.783199   18.615038 
C       -6.464146    7.315843   19.732482 
H       -5.516006    7.460886   20.261700 
H       -3.019083   16.226202   17.354486 
H       -0.410819    5.322455   11.443723 
H       -9.227512    9.843987   16.944769 
H        1.714223    4.446214   20.158370 
H      -13.191440    8.700984   11.756207 
H       -3.145643    1.237616   10.583931 
H       -5.921959    3.553155    2.385445 
H       -4.774123   11.832168   11.868936 
C        1.171031   10.026624   10.797487 
H        2.162818    9.619385   11.025185 
H        0.784640    9.490848    9.922338 
H        1.291962   11.077111   10.508767 
C       -1.177808   10.418530   11.615668 
H       -1.615040    9.796173   10.823723 
H       -1.858660   10.395076   12.475887 
H       -1.127706   11.450896   11.243783 
C        1.525870    6.219115   16.310876 
H        2.234134    7.034460   16.124179 
H        1.570236    5.971730   17.377790 



S42 
 

H        1.859896    5.342723   15.740091 
C       -0.895400    5.533056   16.359862 
H       -0.880494    5.458833   17.452825 
H       -1.916974    5.785079   16.050517 
H       -0.639586    4.542961   15.960912 
C        0.283989   13.520565   19.989764 
H       -0.328035   14.263758   20.514739 
H        0.771258   12.900226   20.752033 
H        1.064366   14.063104   19.444949 
C       -1.685270   11.972667   19.874965 
H       -2.239136   11.249629   19.265569 
H       -1.278712   11.441629   20.743330 
H       -2.405685   12.712347   20.247948 
C       -0.565484   14.386379   13.246090 
H       -0.451304   14.058526   12.205560 
H       -1.043939   15.373425   13.235946 
H        0.436613   14.503880   13.674527 
C       -2.775635   13.170698   13.394343 
H       -3.369067   14.092740   13.412467 
H       -2.665202   12.868607   12.345931 
H       -3.342517   12.392069   13.919891 
C        1.881975    9.379103   21.049314 
H        2.091913   10.455388   21.023714 
H        1.554134    9.120670   22.062183 
H        2.829687    8.858257   20.867816 
C        1.398367    9.314656   18.590465 
H        1.762912   10.346123   18.519641 
H        2.239301    8.648694   18.357879 
H        0.639839    9.171195   17.812749 
C       -3.106344    4.124066   19.419234 
H       -2.719336    3.273238   19.992849 
H       -4.182918    3.964586   19.294903 
H       -2.644944    4.106977   18.425380 
C       -3.454578    5.417741   21.545764 
H       -2.908095    4.704200   22.175622 
H       -3.424436    6.398758   22.031075 
H       -4.504368    5.099167   21.507638 
C       -5.864878   13.286223   18.624554 
H       -6.168951   13.154163   19.669335 
H       -5.139989   14.108294   18.582373 
H       -6.752155   13.594065   18.057450 
C       -4.803987   12.266452   16.588240 
H       -4.097031   13.102211   16.545884 
H       -4.311910   11.381677   16.169328 
H       -5.663246   12.518771   15.951393 
C       -7.546461    7.058784   20.789695 
H       -8.514578    6.833665   20.326350 
H       -7.270633    6.201527   21.415446 
H       -7.686578    7.924947   21.446118 
C       -6.303266    6.086954   18.829298 
H       -7.209581    5.907652   18.237019 
H       -5.464004    6.209708   18.134751 
H       -6.119688    5.190556   19.434915 
C       -4.543798   11.280699    6.405311 
H       -5.580967   11.337690    6.062581 

H       -4.248795   12.268609    6.781373 
H       -3.920354   11.052577    5.531125 
C       -2.849806   10.029488    7.754861 
H       -2.351029    9.687981    6.840814 
H       -2.368911   10.969967    8.050771 
H       -2.660302    9.287050    8.537963 
C       -8.835464    8.833092   11.152052 
H       -9.875851    8.498438   11.227846 
H       -8.223914    7.983731   10.826898 
H       -8.502230    9.131637   12.156390 
C       -9.617994   11.159784   10.624242 
H       -9.364081   11.489973   11.638811 
H       -9.541178   12.032528    9.965543 
H      -10.663942   10.830350   10.638470 
C       -4.302619    8.273680    2.908614 
H       -3.700193    9.170964    3.093304 
H       -3.669522    7.559219    2.369226 
H       -5.130725    8.550506    2.246083 
C       -3.629259    7.269190    5.121179 
H       -3.971760    6.926154    6.104991 
H       -3.068670    6.448159    4.656610 
H       -2.937454    8.107674    5.270925 
C      -10.351810    5.688388    4.308232 
H      -10.365648    5.063943    3.405903 
H      -11.319643    5.571746    4.811430 
H      -10.261907    6.733587    3.994114 
C       -9.501462    3.872919    5.812889 
H       -8.701769    3.530650    6.477500 
H      -10.429154    3.889241    6.396426 
H       -9.630890    3.122814    5.022927 
C      -11.371086    4.129657   13.281934 
H      -12.040967    4.721701   13.917766 
H      -11.992414    3.524700   12.611274 
H      -10.810241    3.445443   13.930588 
C       -9.497676    5.822109   13.440209 
H      -10.070312    6.506798   14.077044 
H       -8.944726    5.142977   14.099353 
H       -8.771369    6.417299   12.873123 
C      -10.761363    7.945441    7.311141 
H      -10.666953    7.932305    6.219079 
H      -11.203809    8.908758    7.596570 
H       -9.752102    7.906234    7.738990 
C      -12.996287    6.805167    7.128519 
H      -12.885338    6.707865    6.042205 
H      -13.644298    5.993306    7.477839 
H      -13.519092    7.749887    7.318418 
C       -4.713890    3.833544    6.701022 
H       -5.007276    4.318480    5.762976 
H       -4.384683    4.613459    7.397766 
H       -3.861541    3.179034    6.477556 
C       -6.297671    1.915144    6.323663 
H       -5.509782    1.151413    6.294122 
H       -7.228135    1.428303    6.637598 
H       -6.442807    2.297214    5.306702 
C       -7.655446    0.549845   12.671143 



S43 
 

H       -6.757227    0.302619   13.249164 
H       -8.504698    0.538115   13.364235 
H       -7.804227   -0.248236   11.935018 
C       -7.265623    3.008633   13.053750 
H       -8.048863    3.003430   13.822580 
H       -6.303202    2.838771   13.553568 
H       -7.238946    4.005040   12.595889 
  
5 
 
SCF (wB97x) =   -8713.99975331 
E(SCF)+ZPE(0 K)=   -8712.027585 
H(298 K)=   -8711.916581 
G(298 K)=   -8712.173729 
Lowest Frequency = 9.1759cm-1 
 
Pd       11.737350    3.778833    6.636813 
H       12.233094    3.345253    5.062417 
H       12.552957    3.245777    8.043947 
H       10.373192    4.717221    6.983296 
N        8.912150    4.140103    3.821969 
C        7.771531    4.731769    3.489893 
C        7.419612    6.046872    3.848863 
H        6.436267    6.372908    3.529396 
C        8.257988    7.053526    4.365766 
N        9.463659    6.836362    4.872498 
C        6.772134    3.984163    2.629701 
H        7.150037    3.875555    1.606906 
H        5.819948    4.517563    2.589638 
H        6.601437    2.973535    3.013913 
C        7.731770    8.472514    4.282577 
H        7.842206    8.996364    5.237087 
H        6.679356    8.480785    3.991285 
H        8.299573    9.044506    3.539705 
C        9.246261    2.911352    3.170428 
C        9.825604    2.954073    1.891291 
C       10.072691    1.755288    1.225107 
H       10.503776    1.788955    0.224412 
C        9.774161    0.519742    1.799870 
C        9.269341    0.506526    3.098274 
H        9.056649   -0.447932    3.579388 
C        9.004576    1.684239    3.800656 
C       10.299800    7.962166    5.154395 
C       10.337133    8.522726    6.439556 
C       11.174161    9.613794    6.674230 
H       11.197980   10.050545    7.672596 
C       11.974822   10.157744    5.671787 
C       11.916017    9.583562    4.402938 
H       12.527758    9.996906    3.600753 
C       11.098253    8.488148    4.126801 
N       15.308554    3.757907    4.842266 
C       16.565680    3.402532    5.045497 
C       16.952767    2.213347    5.694158 
H       18.020811    2.077954    5.818248 
C       16.160815    1.100369    6.024209 

N       14.829739    1.068840    5.988607 
C       17.684516    4.275959    4.517770 
H       17.658014    4.308224    3.422808 
H       18.659430    3.897473    4.831639 
H       17.572502    5.307150    4.867182 
C       16.925149   -0.153430    6.403420 
H       16.676420   -0.470314    7.419604 
H       18.001954    0.015918    6.344005 
H       16.663411   -0.984576    5.740685 
C       15.030794    4.863817    3.974213 
C       14.839212    4.617029    2.599647 
C       14.549504    5.692853    1.758851 
H       14.402800    5.514106    0.695147 
C       14.451350    6.985916    2.254821 
H       14.232882    7.814412    1.584666 
C       14.626376    7.212257    3.613003 
H       14.528318    8.222576    4.004716 
C       14.913265    6.166490    4.492627 
C       14.928746    3.217995    2.005931 
H       15.228512    2.528485    2.802465 
C       13.560554    2.761244    1.485655 
H       12.810108    2.743375    2.285778 
H       13.625964    1.753269    1.057647 
H       13.192459    3.433381    0.699691 
C       15.989057    3.127825    0.901565 
H       15.729486    3.755926    0.040830 
H       16.079447    2.095152    0.543104 
H       16.973518    3.447224    1.262648 
C       15.051497    6.464554    5.976716 
H       15.371892    5.547774    6.484785 
C       16.098708    7.547955    6.262998 
H       17.082792    7.289062    5.853435 
H       16.203752    7.685935    7.345647 
H       15.803996    8.513733    5.833377 
C       13.693214    6.870883    6.557160 
H       13.316886    7.783659    6.079686 
H       13.781754    7.052922    7.632303 
H       12.947107    6.078779    6.407462 
C       14.189957   -0.207692    6.138082 
C       13.922529   -0.741407    7.412102 
C       13.380895   -2.026337    7.499521 
H       13.181178   -2.453485    8.480311 
C       13.087467   -2.763253    6.363600 
H       12.675318   -3.765581    6.450495 
C       13.297759   -2.200632    5.110727 
H       13.030701   -2.770544    4.225561 
C       14.132287    0.048260    8.696099 
H       14.594757    1.007717    8.435324 
C       15.036126   -0.661330    9.712328 
H       14.586310   -1.599366   10.059286 
H       15.184441   -0.022717   10.591662 
H       16.022902   -0.900448    9.301903 
C       12.766508    0.336120    9.330256 
H       12.118646    0.871094    8.628308 
H       12.874694    0.944312   10.237453 



S44 
 

H       12.263894   -0.596967    9.614386 
N       12.171542    5.013076   10.607611 
C       11.592147    5.104020   11.799521 
C       10.294741    4.654374   12.096421 
H        9.958990    4.842241   13.109563 
C        9.364076    4.007224   11.264482 
N        9.595649    3.636210   10.011199 
C       12.357368    5.730857   12.949011 
H       13.313238    5.216705   13.096957 
H       11.782448    5.676170   13.875447 
H       12.593446    6.780159   12.744930 
C        8.001878    3.740781   11.874532 
H        7.227272    4.276473   11.314403 
H        7.968675    4.069044   12.915174 
H        7.744599    2.678069   11.830850 
C       13.468033    5.598679   10.446702 
C       14.618994    4.799484   10.543267 
C       15.868257    5.396163   10.386947 
H       16.759779    4.774406   10.466548 
C       16.008230    6.762747   10.142890 
C       14.851028    7.530100   10.042176 
H       14.934194    8.597221    9.837255 
C       13.579296    6.969147   10.176028 
C        8.560359    2.923987    9.319680 
C        7.607300    3.602288    8.545957 
C        6.611842    2.862686    7.903962 
H        5.866481    3.397596    7.314037 
C        6.542131    1.476328    7.995285 
C        7.502614    0.824792    8.768003 
H        7.463313   -0.259743    8.866812 
C        8.505109    1.523302    9.437067 
Zn       10.086118    4.950622    5.209944 
Zn       11.319719    4.044061    9.075675 
Zn       13.785413    2.740316    5.674154 
C       13.835248   -0.920884    4.971225 
C       14.020573   -0.314613    3.583402 
H       13.834239    0.763632    3.674558 
C       13.010961   -0.855638    2.568911 
H       13.220731   -1.897511    2.296527 
H       11.989178   -0.793689    2.956611 
H       13.055069   -0.265256    1.647103 
C       15.447173   -0.489756    3.044656 
H       15.518525   -0.086075    2.026193 
H       16.189136    0.031820    3.657402 
H       15.715837   -1.553244    3.004431 
C       11.080911    7.871486    2.751404 
H       11.518597    6.865616    2.772782 
H       10.064233    7.772082    2.353528 
H       11.667608    8.472238    2.049344 
C        9.483901    7.961199    7.546252 
H        8.423271    7.926310    7.268647 
H        9.781667    6.932786    7.780128 
H        9.577894    8.562120    8.456774 
C       12.910622   11.304980    5.960773 
H       13.052537   11.937964    5.078503 

H       12.533300   11.934408    6.773462 
H       13.899129   10.935468    6.263066 
C       10.184342    4.272528    1.252133 
H        9.330891    4.958849    1.199260 
H       10.965995    4.782987    1.829811 
H       10.563086    4.119789    0.236297 
C        8.443902    1.641111    5.196274 
H        9.129670    2.107048    5.916703 
H        7.495858    2.187218    5.269193 
H        8.270345    0.609436    5.519735 
C        9.959240   -0.757866    1.018762 
H       10.873854   -0.731162    0.416288 
H       10.016863   -1.628125    1.680763 
H        9.118841   -0.919865    0.332442 
C       14.507231    3.321533   10.811705 
H       13.885704    3.111033   11.690470 
H       14.043987    2.812372    9.958779 
H       15.495294    2.878508   10.974283 
C       12.347170    7.817159    9.988008 
H       11.759390    7.453181    9.135896 
H       11.685757    7.798361   10.862349 
H       12.619898    8.858447    9.787472 
C       17.376690    7.378843    9.986114 
H       17.311259    8.462580    9.845092 
H       18.000394    7.191547   10.867808 
H       17.902234    6.960500    9.119317 
C        7.594647    5.104743    8.411330 
H        8.355484    5.577523    9.036938 
H        7.781311    5.404051    7.372150 
H        6.615865    5.510047    8.695857 
C        5.477591    0.701482    7.260024 
H        5.259155   -0.248962    7.757878 
H        4.544976    1.271413    7.190982 
H        5.798213    0.471232    6.235795 
C        9.470517    0.788973   10.331273 
H        9.201637    0.908320   11.389600 
H        9.472983   -0.282509   10.107912 
H       10.489055    1.168309   10.221810 
  
5-theta30 
 
SCF (wB97x) =   -8713.89760241 
 
Pd       11.737350    3.778833    6.636813 
H       12.609858    3.208565    5.285517 
H       12.191812    3.479760    8.259591 
H       10.353925    4.740282    6.484167 
N        8.912150    4.140103    3.821969 
C        7.771531    4.731769    3.489893 
C        7.419612    6.046872    3.848863 
H        6.436267    6.372908    3.529396 
C        8.257988    7.053526    4.365766 
N        9.463659    6.836362    4.872498 
C        6.772134    3.984163    2.629701 
H        7.150037    3.875555    1.606906 



S45 
 

H        5.819948    4.517563    2.589638 
H        6.601437    2.973535    3.013913 
C        7.731770    8.472514    4.282577 
H        7.842206    8.996364    5.237087 
H        6.679356    8.480785    3.991285 
H        8.299573    9.044506    3.539705 
C        9.246261    2.911352    3.170428 
C        9.825604    2.954073    1.891291 
C       10.072691    1.755288    1.225107 
H       10.503776    1.788955    0.224412 
C        9.774161    0.519742    1.799870 
C        9.269341    0.506526    3.098274 
H        9.056649   -0.447932    3.579388 
C        9.004576    1.684239    3.800656 
C       10.299800    7.962166    5.154395 
C       10.337133    8.522726    6.439556 
C       11.174161    9.613794    6.674230 
H       11.197980   10.050545    7.672596 
C       11.974822   10.157744    5.671787 
C       11.916017    9.583562    4.402938 
H       12.527758    9.996906    3.600753 
C       11.098253    8.488148    4.126801 
N       15.308554    3.757907    4.842266 
C       16.565680    3.402532    5.045497 
C       16.952767    2.213347    5.694158 
H       18.020811    2.077954    5.818248 
C       16.160815    1.100369    6.024209 
N       14.829739    1.068840    5.988607 
C       17.684516    4.275959    4.517770 
H       17.658014    4.308224    3.422808 
H       18.659430    3.897473    4.831639 
H       17.572502    5.307150    4.867182 
C       16.925149   -0.153430    6.403420 
H       16.676420   -0.470314    7.419604 
H       18.001954    0.015918    6.344005 
H       16.663411   -0.984576    5.740685 
C       15.030794    4.863817    3.974213 
C       14.839212    4.617029    2.599647 
C       14.549504    5.692853    1.758851 
H       14.402800    5.514106    0.695147 
C       14.451350    6.985916    2.254821 
H       14.232882    7.814412    1.584666 
C       14.626376    7.212257    3.613003 
H       14.528318    8.222576    4.004716 
C       14.913265    6.166490    4.492627 
C       14.928746    3.217995    2.005931 
H       15.228512    2.528485    2.802465 
C       13.560554    2.761244    1.485655 
H       12.810108    2.743375    2.285778 
H       13.625964    1.753269    1.057647 
H       13.192459    3.433381    0.699691 
C       15.989057    3.127825    0.901565 
H       15.729486    3.755926    0.040830 
H       16.079447    2.095152    0.543104 
H       16.973518    3.447224    1.262648 

C       15.051497    6.464554    5.976716 
H       15.371892    5.547774    6.484785 
C       16.098708    7.547955    6.262998 
H       17.082792    7.289062    5.853435 
H       16.203752    7.685935    7.345647 
H       15.803996    8.513733    5.833377 
C       13.693214    6.870883    6.557160 
H       13.316886    7.783659    6.079686 
H       13.781754    7.052922    7.632303 
H       12.947107    6.078779    6.407462 
C       14.189957   -0.207692    6.138082 
C       13.922529   -0.741407    7.412102 
C       13.380895   -2.026337    7.499521 
H       13.181178   -2.453485    8.480311 
C       13.087467   -2.763253    6.363600 
H       12.675318   -3.765581    6.450495 
C       13.297759   -2.200632    5.110727 
H       13.030701   -2.770544    4.225561 
C       14.132287    0.048260    8.696099 
H       14.594757    1.007717    8.435324 
C       15.036126   -0.661330    9.712328 
H       14.586310   -1.599366   10.059286 
H       15.184441   -0.022717   10.591662 
H       16.022902   -0.900448    9.301903 
C       12.766508    0.336120    9.330256 
H       12.118646    0.871094    8.628308 
H       12.874694    0.944312   10.237453 
H       12.263894   -0.596967    9.614386 
N       12.171542    5.013076   10.607611 
C       11.592147    5.104020   11.799521 
C       10.294741    4.654374   12.096421 
H        9.958990    4.842241   13.109563 
C        9.364076    4.007224   11.264482 
N        9.595649    3.636210   10.011199 
C       12.357368    5.730857   12.949011 
H       13.313238    5.216705   13.096957 
H       11.782448    5.676170   13.875447 
H       12.593446    6.780159   12.744930 
C        8.001878    3.740781   11.874532 
H        7.227272    4.276473   11.314403 
H        7.968675    4.069044   12.915174 
H        7.744599    2.678069   11.830850 
C       13.468033    5.598679   10.446702 
C       14.618994    4.799484   10.543267 
C       15.868257    5.396163   10.386947 
H       16.759779    4.774406   10.466548 
C       16.008230    6.762747   10.142890 
C       14.851028    7.530100   10.042176 
H       14.934194    8.597221    9.837255 
C       13.579296    6.969147   10.176028 
C        8.560359    2.923987    9.319680 
C        7.607300    3.602288    8.545957 
C        6.611842    2.862686    7.903962 
H        5.866481    3.397596    7.314037 
C        6.542131    1.476328    7.995285 



S46 
 

C        7.502614    0.824792    8.768003 
H        7.463313   -0.259743    8.866812 
C        8.505109    1.523302    9.437067 
Zn       10.086118    4.950622    5.209944 
Zn       11.319719    4.044061    9.075675 
Zn       13.785413    2.740316    5.674154 
C       13.835248   -0.920884    4.971225 
C       14.020573   -0.314613    3.583402 
H       13.834239    0.763632    3.674558 
C       13.010961   -0.855638    2.568911 
H       13.220731   -1.897511    2.296527 
H       11.989178   -0.793689    2.956611 
H       13.055069   -0.265256    1.647103 
C       15.447173   -0.489756    3.044656 
H       15.518525   -0.086075    2.026193 
H       16.189136    0.031820    3.657402 
H       15.715837   -1.553244    3.004431 
C       11.080911    7.871486    2.751404 
H       11.518597    6.865616    2.772782 
H       10.064233    7.772082    2.353528 
H       11.667608    8.472238    2.049344 
C        9.483901    7.961199    7.546252 
H        8.423271    7.926310    7.268647 
H        9.781667    6.932786    7.780128 
H        9.577894    8.562120    8.456774 
C       12.910622   11.304980    5.960773 
H       13.052537   11.937964    5.078503 
H       12.533300   11.934408    6.773462 
H       13.899129   10.935468    6.263066 
C       10.184342    4.272528    1.252133 
H        9.330891    4.958849    1.199260 
H       10.965995    4.782987    1.829811 
H       10.563086    4.119789    0.236297 
C        8.443902    1.641111    5.196274 
H        9.129670    2.107048    5.916703 
H        7.495858    2.187218    5.269193 
H        8.270345    0.609436    5.519735 
C        9.959240   -0.757866    1.018762 
H       10.873854   -0.731162    0.416288 
H       10.016863   -1.628125    1.680763 
H        9.118841   -0.919865    0.332442 
C       14.507231    3.321533   10.811705 
H       13.885704    3.111033   11.690470 
H       14.043987    2.812372    9.958779 
H       15.495294    2.878508   10.974283 
C       12.347170    7.817159    9.988008 
H       11.759390    7.453181    9.135896 
H       11.685757    7.798361   10.862349 
H       12.619898    8.858447    9.787472 
C       17.376690    7.378843    9.986114 
H       17.311259    8.462580    9.845092 
H       18.000394    7.191547   10.867808 
H       17.902234    6.960500    9.119317 
C        7.594647    5.104743    8.411330 
H        8.355484    5.577523    9.036938 

H        7.781311    5.404051    7.372150 
H        6.615865    5.510047    8.695857 
C        5.477591    0.701482    7.260024 
H        5.259155   -0.248962    7.757878 
H        4.544976    1.271413    7.190982 
H        5.798213    0.471232    6.235795 
C        9.470517    0.788973   10.331273 
H        9.201637    0.908320   11.389600 
H        9.472983   -0.282509   10.107912 
H       10.489055    1.168309   10.221810 
 
5-theta35 
 
SCF (wB97x) =   -8713.96300869 
 
Pd       11.737350    3.778833    6.636813 
H       12.493563    3.248723    5.201682 
H       12.308756    3.403954    8.206001 
H       10.346915    4.742271    6.631561 
N        8.912150    4.140103    3.821969 
C        7.771531    4.731769    3.489893 
C        7.419612    6.046872    3.848863 
H        6.436267    6.372908    3.529396 
C        8.257988    7.053526    4.365766 
N        9.463659    6.836362    4.872498 
C        6.772134    3.984163    2.629701 
H        7.150037    3.875555    1.606906 
H        5.819948    4.517563    2.589638 
H        6.601437    2.973535    3.013913