Aggregation control of copper (I) thiolates through substituent size and ancillary chelate ligands: closely related mono-, di-, tri-, and tetranuclear complexes

摘要

The choice of thiolates and of ancillary nitrogen chelate ligands N^ N determines the aggregation state of copper(I) thiolate compounds [(RS)_x Cy_y(N^N)_z]~k. Starting from electrogenerated [(RS)Cu]_n, the species obtained an structurally characterized include(i) mononuclear (RS)Cu(Me_4phen), Me_4phen=3,4,7,8-tetramethyl-1,10-phenanthroline, with 2,6-diorganophenyl thiolates RS~-, (ii) dinuclear [(#mu#-RS)Cu(Me_4phen)]_2 mde_2phen=2,9-dimethyl-1,10-phenanthroline, with R=phenyl or o-tolyl, (iii) trinuclear [(#mu#-RS)Cu(Me_4phen)]_2 with R=mesityl, (iv) tetranuclear (#mu#-RS)_4Cu_4(bpy)_2 with R=2,4,6-i-Pr_3C_6H_2, and (v) the tetranuclear dianion [(#mu#-RS)_6Cu_4]~(2-) where the added dchelate ligand N^N=bis (2-imidazolyl)ketone occurs in the [(N^N)_2Cu]~+ counterions. The new trinuclear (#mu#-MesS)_3Cu_3(Me_4phen)_2 exhibits an unsymmetrical Cu_3S_3 six-memberded ring in which the dicoordinate copper (I) center has a nearly linear configuration (angle S-Cu -S 173.93(13) deg). Both tetracoordinate copper (I) atom sites exhibit a characteristic distortion from a tetrahedral towards a trigonal pyramidal CuN_2S_2 arrangement which is reminiscent of the geometry observed for the rhombic variants of type 1 Cu centers in blue copper proteins