Please use this identifier to cite or link to this item: https://doi.org/10.1016/S0020-1693(03)00198-1
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)
Authors: Anjali, K.S.
Vittal, J.J. 
Dean, P.A.W.
Keywords: 4-Pyridinethiol
4-Pyridiniumthiolate
Crystal structures
Group 12 metal complexes
Metal NMR
Pyridine-4-thiol
Pyridine-4-thiolate
Thermogravimetric analysis
Issue Date: 22-Jul-2003
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
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.
Source Title: Inorganica Chimica Acta
URI: http://scholarbank.nus.edu.sg/handle/10635/95016
ISSN: 00201693
DOI: 10.1016/S0020-1693(03)00198-1
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.

SCOPUSTM   
Citations

14
checked on Jul 17, 2018

WEB OF SCIENCETM
Citations

17
checked on Jun 27, 2018

Page view(s)

33
checked on Jul 6, 2018

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.