Understanding the solution and solid-state structures of Pd and Pt PSiP pincer-supported hydrides

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dc.contributor.authorSuh, HWen_AU
dc.contributor.authorBalcells, Den_AU
dc.contributor.authorEdwards, AJen_AU
dc.contributor.authorGuard, LMen_AU
dc.contributor.authorHazari, Nen_AU
dc.contributor.authorMader, EAen_AU
dc.contributor.authorMercado, BQen_AU
dc.contributor.authorRepisky, Men_AU
dc.date.accessioned2025-10-17T03:01:17Zen_AU
dc.date.available2025-10-17T03:01:17Zen_AU
dc.date.issued2015-11-19en_AU
dc.date.statistics2025-10-15en_AU
dc.description.abstractThe PSiP pincer-supported complex (CyPSiP)PdH [CyPSiP = Si(Me)(2-PCy2-C6H4)2] has been implicated as a crucial intermediate in carboxylation of both allenes and boranes. At this stage, however, there is uncertainty regarding the exact structure of (CyPSiP)PdH, especially in solution. Previously, both a Pd(II) structure with a terminal Pd hydride and a Pd(0) structure featuring an η2-silane have been proposed. In this contribution, a range of techniques were used to establish that (CyPSiP)PdH and the related Pt species, (CyPSiP)PtH, are true M(II) hydrides in both the solid state and solution. The single-crystal X-ray structures of (CyPSiP)MH (M = Pd and Pt) and the related species (iPrPSiP)PdH [iPrPSiP = Si(Me)(2-PiPr2-C6H4)2] are in agreement with the presence of a terminal metal hydride, and the exact geometry of (CyPSiP)PtH was confirmed using neutron diffraction. The 1H and 29Si{1H}NMR chemical shifts of (CyPSiP)MH (M = Pd and Pt) are consistent with a structure containing a terminal hydride, especially when compared to the chemical shifts of related pincer-supported complexes. In fact, in this work, two general trends relating to the 1H NMR chemical shifts of group 10 pincer-supported terminal hydrides were elucidated: (i) the hydride shift moves downfield from Ni to Pd to Pt and (ii) the hydride shift moves downfield with more trans-influencing pincer central donors. DFT calculations indicate that structures containing a M(II) hydride are lower in energy than the corresponding η2-silane isomers. Furthermore, the calculated NMR chemical shifts of the M(II) hydrides using a relativistic four-component methodology incorporating all significant scalar and spin-orbit corrections are consistent with those observed experimentally. Finally, in situ X-ray absorption spectroscopy (XAS) was used to provide further support that (CyPSiP)MH exist as M(II) hydrides in solution. © 2015 American Chemical Society.en_AU
dc.description.sponsorshipN.H. is grateful to the National Science Foundation for support through Grant CHE-1150826. D.B. acknowledges support from the Norwegian Research Council through the Center of Excellence for Theoretical and Computational Chemistry (CTCC) (Grant No. 179568/V30) and the Norwegian Metacenter for Computational Science (NOTUR; Grant nn4654k). D.B. also thanks the EU REA for a Marie Curie Fellowship (Grant CompuWOC/618303). The Australian Nuclear Science and Technology Organization is thanked for the award of neutron beam time on KOALA to proposal P3757. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. N.H. is a fellow of the Alfred P. Sloan Foundation and a Camille and Henry-Dreyfus Foundation Teacher Scholar. E.A.M. thanks Drs. J. Katsoudas and J. Wright for thoughtful discussions.en_AU
dc.format.mediumPrint-Electronicen_AU
dc.identifier.citationSuh, H.-W., Balcells, D., Edwards, A. J., Guard, L. M., Hazari, N., Mader, E. A., Mercado, B. Q., & Repisky, M. (2015). Understanding the solution and solid-state structures of Pd and Pt PSiP pincer-supported hydrides. Inorganic Chemistry, 54(23), 11411–11422. doi:10.1021/acs.inorgchem.5b02073en_AU
dc.identifier.issn0020-1669en_AU
dc.identifier.issn1520-510Xen_AU
dc.identifier.issue23en_AU
dc.identifier.journaltitleInorganic Chemistryen_AU
dc.identifier.pagination11411-11422en_AU
dc.identifier.urihttps://doi.org/10.1021/acs.inorgchem.5b02073en_AU
dc.identifier.urihttps://apo.ansto.gov.au/handle/10238/16618en_AU
dc.identifier.volume54en_AU
dc.languageEnglishen_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectHydridesen_AU
dc.subjectPalladiumen_AU
dc.subjectPlatinumen_AU
dc.subjectSiliconen_AU
dc.subjectSolutionsen_AU
dc.subjectAnionsen_AU
dc.subjectLigandsen_AU
dc.subjectCrystal structureen_AU
dc.subjectTemperature rangeen_AU
dc.titleUnderstanding the solution and solid-state structures of Pd and Pt PSiP pincer-supported hydridesen_AU
dc.typeJournal Articleen_AU
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