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Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds

The X-ray structural chemistry of zinc and cadmium 1,1-dithiolates (for example, xanthate, dithiophosphate and dithiocarbamate) with potentially bridging bipyridyl-type ligands (for example, 4,40-bipyridine) is reviewed. For zinc, the xanthates and dithiophosphates uniformly form one-dimensional co...

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Main Author: Tiekink, Edward R. T. *
Format: Article
Language:English
Published: MDPI 2018
Subjects:
QD Chemistry
Online Access:http://eprints.sunway.edu.my/734/1/Tiekink%20Perplexing%20coordination%20behaviour.pdf
http://eprints.sunway.edu.my/734/
http://dx.doi.org/10.3390/cryst8010018
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spelling my.sunway.eprints.7342020-10-07T09:14:11Z http://eprints.sunway.edu.my/734/ Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds Tiekink, Edward R. T. * QD Chemistry The X-ray structural chemistry of zinc and cadmium 1,1-dithiolates (for example, xanthate, dithiophosphate and dithiocarbamate) with potentially bridging bipyridyl-type ligands (for example, 4,40-bipyridine) is reviewed. For zinc, the xanthates and dithiophosphates uniformly form one-dimensional coordination polymers, whereas the zinc dithiocarbamates are always zero-dimensional, reflecting the exceptional chelating ability of dithiocarbamate ligands compared with xanthates and dithiophosphates. For cadmium, one-dimensional coordination polymers are usually found, reflecting the larger size of cadmium compared with zinc, but zero-dimensional aggregates are sometimes found. Steric effects associated with the 1,1-dithiolate-bound R groups are shown to influence supramolecular aggregation and, when formed, polymer topology in order to reduce steric hindrance; the nature of the bipyridyl-type ligand can also be influential. For the dithiocarbamates of both zinc and cadmium, in instances where the dithiocarbamate ligand is functionalised with hydrogen bonding potential, extended supramolecular architectures are often formed via hydrogen bonding interactions. Of particular interest is the observation that the bipyridyl-type ligands do not always bridge zinc or cadmium 1,1-dithiolates, being monodentate instead, often in the presence of hydrogen bonding. Thus, hydroxyl-O–H . . . N(pyridyl) hydrogen bonds are sometimes formed in preference toM N(pyridyl) coordinate-bonds, suggesting a competition between the two modes of association. MDPI 2018-01 Article PeerReviewed text en http://eprints.sunway.edu.my/734/1/Tiekink%20Perplexing%20coordination%20behaviour.pdf Tiekink, Edward R. T. * (2018) Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds. Crystals, 8 (1). p. 18. ISSN 2073-4352 http://dx.doi.org/10.3390/cryst8010018 doi:10.3390/cryst8010018
institution Sunway University
building Sunway Campus Library
collection Institutional Repository
continent Asia
country Malaysia
content_provider Sunway University
content_source Sunway Institutional Repository
url_provider http://eprints.sunway.edu.my/
language English
topic QD Chemistry
spellingShingle QD Chemistry
Tiekink, Edward R. T. *
Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds
description The X-ray structural chemistry of zinc and cadmium 1,1-dithiolates (for example, xanthate, dithiophosphate and dithiocarbamate) with potentially bridging bipyridyl-type ligands (for example, 4,40-bipyridine) is reviewed. For zinc, the xanthates and dithiophosphates uniformly form one-dimensional coordination polymers, whereas the zinc dithiocarbamates are always zero-dimensional, reflecting the exceptional chelating ability of dithiocarbamate ligands compared with xanthates and dithiophosphates. For cadmium, one-dimensional coordination polymers are usually found, reflecting the larger size of cadmium compared with zinc, but zero-dimensional aggregates are sometimes found. Steric effects associated with the 1,1-dithiolate-bound R groups are shown to influence supramolecular aggregation and, when formed, polymer topology in order to reduce steric hindrance; the nature of the bipyridyl-type ligand can also be influential. For the dithiocarbamates of both zinc and cadmium, in instances where the dithiocarbamate ligand is functionalised with hydrogen bonding potential, extended supramolecular architectures are often formed via hydrogen bonding interactions. Of particular interest is the observation that the bipyridyl-type ligands do not always bridge zinc or cadmium 1,1-dithiolates, being monodentate instead, often in the presence of hydrogen bonding. Thus, hydroxyl-O–H . . . N(pyridyl) hydrogen bonds are sometimes formed in preference toM N(pyridyl) coordinate-bonds, suggesting a competition between the two modes of association.
format Article
author Tiekink, Edward R. T. *
author_facet Tiekink, Edward R. T. *
author_sort Tiekink, Edward R. T. *
title Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds
title_short Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds
title_full Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds
title_fullStr Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds
title_full_unstemmed Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds
title_sort perplexing coordination behaviour of potentially bridging bipyridyl-type ligands in the coordination chemistry of zinc and cadmium 1,1-dithiolate compounds
publisher MDPI
publishDate 2018
url http://eprints.sunway.edu.my/734/1/Tiekink%20Perplexing%20coordination%20behaviour.pdf
http://eprints.sunway.edu.my/734/
http://dx.doi.org/10.3390/cryst8010018
_version_ 1680323392706707456
score 13.211869

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