Comparisons of zinc with cadmium in N2S2 coordination and as S-bonded adducts to tungsten carbonyls

Jason A. Denny; William S. Foley; Elky Almaraz; Joseph H. Reibenspies; Nattamai Bhuvanesh; Marcetta Y. Darensbourg

doi:10.1039/C1DT11336D

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Comparisons of zinc with cadmium in N₂S₂ coordination and as S-bonded adducts to tungsten carbonyls†

Jason A. Denny,^a William S. Foley,^a Elky Almaraz,^a Joseph H. Reibenspies,^a Nattamai Bhuvanesh^a and Marcetta Y. Darensbourg*^a

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* Corresponding authors

^a Texas A&M University, 3255 TAMU, College Station, TX, USA
E-mail: marcetta@mail.chem.tamu.edu
Fax: 979-845-0158
Tel: 979-845-5417

Abstract

The synthesis and characterization of bis-mercaptoethanediazaheptane cadmium(II) is reported and compared to the analogous zinc complex. Of significance is the dimeric form of the [Zn(N₂S₂)]₂ complex achieves penta-coordination about zinc through a bridging thiolate whereas cadmium engages two thiolate as S-bridges resulting in hexa-coordination about cadmium within a coordination polymer whose X-ray crystal structure is reported here. In the presence of W(CO)₅, this polymer breaks up, generating dimeric [Cd(N₂S₂)]₂ with two W(CO)₅ units appended to the terminal thiolates, a feat that is not observed for the zinc dimer analogue. The greater thiophilicity of cadmium over zinc is noted in several features of these complexes.

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Article information

DOI: https://doi.org/10.1039/C1DT11336D
Article type: Paper
Submitted: 14 Jul 2011
Accepted: 05 Oct 2011
First published: 15 Nov 2011

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Dalton Trans., 2012,41, 143-148

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Comparisons of zinc with cadmium in N₂S₂ coordination and as S-bonded adducts to tungsten carbonyls

J. A. Denny, W. S. Foley, E. Almaraz, J. H. Reibenspies, N. Bhuvanesh and M. Y. Darensbourg, Dalton Trans., 2012, 41, 143 DOI: 10.1039/C1DT11336D

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Dalton Transactions