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Synthesis and X‐ray Characterization of Mono‐ and Polynuclear Thiolatocopper(I) Complexes: The Effect of Steric Bulk on Coordination Number and Nuclearity
Author(s) -
Zeevi Shiri,
Tshuva Edit Y.
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200700710
Subject(s) - chemistry , steric effects , copper , cluster (spacecraft) , crystallography , coordination sphere , substituent , metal , alkyl , stereochemistry , atom (system on chip) , coordination number , coordination complex , crystal structure , ion , organic chemistry , computer science , programming language , embedded system
We have synthesized a number of Cu I complexes of thiophenolato ligands with different alkyl substituents in the ortho positions in a single‐step procedure starting from a readily available copper(I) precursor to evaluate the coordination preferences of the metal atom. In most cases similar reaction conditions led to the formation of two complexes: a mononuclear complex and a polynuclear cluster, as evident from X‐ray crystallography. One dinuclear complex formed has the unique geometry of an L 2 Cu 2 (μ‐L) 2 core that has not previously been observed for related systems. The steric bulk around the metal atom has a clear effect on the coordination sphere of the complex obtained. Ligands with no ortho substituents and those with one substituent with a size varying from methyl to tert ‐butyl all lead to the formation of three‐coordinate complexes for the mononuclear species, and clusters of different sizes where larger substituents lead to larger cages and all copper centers are three‐coordinate as well. The introduction of two methyl substituents (one in each ortho position) leads to either a mononuclear two‐coordinate copper complex or a polynuclear cluster where two copper centers are three‐coordinate and three are two‐coordinate.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)