Abstract
The choice of thiolates and of ancillary N chelate ligands N-N dets. the aggregation state of Cu(I) thiolate compds. [(RS)xCuy(N-N)z]k. Starting from electrogenerated [(RS)Cu]n, the species obtained and structurally characterized include (i) mononuclear (RS)Cu(Me4phen), Me4phen = 3,4,7,8-tetramethyl-1,10-phenanthroline, with 2,6-diorganophenylthiolates RS-, (ii) dinuclear [(m-RS)Cu(Me2phen)]2, Me2phen = 2,9-dimethyl-1,10-phenanthroline, with R = Ph or o-tolyl, (iii) trinuclear (m-RS)3Cu3(Me4phen)2 with R = mesityl, (iv) tetranuclear (m-RS)4Cu4(bpy)2 with R = 2,4,6-i-Pr3C6H2, and (v) the tetranuclear dianion [(m-RS)6Cu4]2- where the added chelate ligand N-N = bis(2-imidazolyl)ketone occurs in the [(N N)2Cu]+ counterions. The new trinuclear (m-MesS)3Cu3(Me4phen)2 exhibits an unsym. Cu3S3 six-membered ring in which the dicoordinate Cu(I) center has a nearly linear configuration (angle S-Cu-S 173.93(13)°). Both tetracoordinate Cu(I) atom sites exhibit a characteristic distortion from a tetrahedral towards a trigonal pyramidal CuN2S2 arrangement which is reminiscent of the geometry obsd. for the rhombic variants of type 1 Cu centers in blue Cu proteins. [on SciFinder(R)]
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