Browsing by Author "Smith, A"

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    Synthesis and characterisation of two new tripodal metalloligands incorporating zinc(II)
    (Springer Nature, 2015-05-06) Fanna, DJ; Smith, A; Zhang, Y; Li, L; Shepherd, ND; Harman, DG; Li, F
    The in situ Schiff base condensation of 2-acetylpyrazine with tris(2-aminoethyl)amine in the presence of zinc(II) perchlorate was carried out in absolute ethanol and 95 % ethanol, respectively. Two new tripodal metalloligands, 1 and 2, were isolated. The formation of complexes 1 and 2 has been verified by NMR, mass spectral studies and X-ray (for 2), with the evidence indicating that a zinc ion is incorporated in the tripodal cavity defined by the tren backbone in each case. However the products differed in the number of Schiff base condensation reactions that had occurred. While the use of absolute ethanol resulted in condensation at all three primary amine sites of tris(2-aminoethyl)amine, employing 95 % ethanol yielded condensation at only one of the primary amine sites. These different outcomes can be ascribed, at least in part, to the effect of the different water contents in the respective reaction solvents resulting in a shift of the dynamic equilibrium involving imine formation towards the precursor amine and ketone reagents. In 1, steric considerations dictate that the three uncoordinated pyrazine nitrogen donors will have their coordination vectors oriented in a mutually divergent manner suitable for coordination to three different metal centres when acting as a metalloligand while for 2, the X-ray structure confirms that the single uncoordinated (pendent) pyrazine nitrogen is also oriented for ready coordination to a second metal centre. © 2015 Springer Science+Business Media Dordrecht