Aggregation control of copper(I) thiolates through substituent size and ancillary chelate ligands: Closely related mono-, di-, tri- and tetranuclear complexes
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Inorganica Chimica Acta 324 (1,2): 336--341 (2001)

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)zk. Starting from electrogenerated (RS)Cun, 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)6Cu42- 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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