Comparative Isotropic Shifts, Redox Potentials, and Ligand Binding Propensities of [1:3] Site-Differentiated Cubane-Type [Fe4Q4]2+ Clusters (Q = S, Se)

Autor:	Chaoyin Zhou, Richard H. Holm
Rok vydání:	1997
Předmět:	Inorganic Chemistry Substitution reaction chemistry.chemical_compound Chemistry Cubane Stereochemistry Ligand Selenide Cluster (physics) Thio Physical and Theoretical Chemistry Redox Non-innocent ligand
Zdroj:	Inorganic Chemistry. 36:4066-4077
ISSN:	1520-510X 0020-1669
DOI:	10.1021/ic970254u
Popis:	The [1:3] site-differentiated cubane-type clusters [Fe4Q4(LS3)Cl]2- (Q = S, Se; LS3 = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzenate(3−)) undergo substitution reactions at the unique iron site with a variety of ligands including thiolates, phenolates, cyclic triamines and a trisulfide, imidazoles, and tertiary phosphines. Reactions are readily followed because of the extreme sensitivity of isotropically shifted resonances to the nature of ligand L‘ in the product clusters [Fe4Q4(LS3)L‘]2-,-. Isotropic shifts and redox potentials are reported for over 40 clusters, including many cluster pairs differing only in the core chalcogenide atom. In this way, comparative properties of sulfide and selenide clusters can be elicited. It is shown that the larger isotropic shifts consistently observed for selenide clusters and dominantly contact in nature arise from larger magnetic susceptibilities, which indicate a lesser extent of antiferromagnetic coupling. It is further demonstrated...
Databáze:	OpenAIRE
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