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|dc.title||Syntheses, characterization and thermal properties of [M(Spy)2(SpyH)2] (M = Cd and Hg; Spy- = pyridine-4-thiolate; SpyH = pyridinium-4-thiolate)) and [M(SpyH)4](ClO4)2 (M = Zn, Cd and Hg)|
|dc.identifier.citation||Anjali, K.S., Vittal, J.J., Dean, P.A.W. (2003-07-22). Syntheses, characterization and thermal properties of [M(Spy)2(SpyH)2] (M = Cd and Hg; Spy- = pyridine-4-thiolate; SpyH = pyridinium-4-thiolate)) and [M(SpyH)4](ClO4)2 (M = Zn, Cd and Hg). Inorganica Chimica Acta 351 (1) : 79-88. ScholarBank@NUS Repository. https://doi.org/10.1016/S0020-1693(03)00198-1|
|dc.description.abstract||The complexes [M(Spy)2(SpyH)2] (Spy-=pyridine-4-thiolate; M=Cd (1) and Hg (2)), of a hitherto unknown type, were prepared by reacting the corresponding metal perchlorates with pyridine-4-thiol in the ratio 1:6 in DMSO-MeOH. The cations [M(SpyH)4]2+ (M=Zn, Cd and Hg) were prepared by a similar reaction, but with M-pySH=1:4 in MeOH, and isolated as their perchlorate salts, 3, 4 and 5. The structures of 1-5 were determined by X-ray crystallography. Both compounds 1 and 2, and the cations in 3-5, are mononuclear complexes in which the metal centre adopts a distorted MS4 kernel. Intermolecular N-H⋯N hydrogen bonds in 1 and 2 lead to one dimensional polymeric chain structures, and similarly N-H⋯O⋯H-N hydrogen bonds between the cations and anions in 3-5 result in chain structures. Thermogravimetric and pyrolysis experiments demonstrate that 1 and 2 decompose to give the corresponding metal sulfides. Metal (113Cd/199Hg (as appropriate)) NMR spectra have been measured for solutions of 4 and 5 with and without incremental addition of NaOMe. Separate signals were not observed for [M(SpyH)n(Spy)4-n](n-2)+, even at the lowest accessible temperature. The changes in metal NMR chemical shift as [M(SpyH)4]2+ is converted into [M(Spy)4]2- are surprisingly small. © 2003 Elsevier B.V. All rights reserved.|
|dc.subject||Group 12 metal complexes|
|dc.description.sourcetitle||Inorganica Chimica Acta|
|Appears in Collections:||Staff Publications|
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