Comparisons of zinc with cadmium in N 2 S 2 coordination and as S-bonded adducts to tungsten carbonyls
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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(N(2)S(2))](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(N(2)S(2))](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.
author list (cited authors)
Denny, J. A., Foley, W. S., Almaraz, E., Reibenspies, J. H., Bhuvanesh, N., & Darensbourg, M. Y.