Metal-mercaptide chemistry. The synthesis and structural characterization of the [Cu(SC6H5)3]2- anion. A rational synthesis and the structure of the [Cu4(SC6H5)6]2- cluster

Abstract

2993center as follows: Mn' contributes 24 electrons, three carbonyl ligands donate 6 electrons, two metal-hydrogen-boron bonds contribute 4 electrons, and the halogen contributes the final 2 electrons for a total of 36.Similar bonding schemes will undoubtedly be found in other metal-borane cluster systems. The presence of multidentate M-H-B bonding to several metal centers may have important implications vis-%-vis our future understanding of the mechanisms of metal cluster growth processes.

Syntheses and X-ray structural analyses of [(C6H5)4As][Sn(EC6H5)3], E = S and Se

“…The dihedral angles Sn-S-CX I-CX6 are 5 1.9, 58.1, and 41.6" so that the phenyl rings are twisted into a propeller-like arrangement. Within the phenyl rings the C-C-C angles are in the range found in other phenylthiolates (4,32,33) and also in triphenylphosphines (34). The S-CXI-CX6 angles of 123.…”

Flexible CuI–Thiolate Clusters with Relevance to Metallothioneins

“…This synthetic protocol led to the formation of a mixture of products such as [Me 4 N] 2 salt of 3 and 4 [34] and both were crystallized out. In another procedure, the use of Cu I as the source material was made and this was treated with KSPh in acetonitrile and the [PPh 4 ] 2 salt of 4 [18] was isolated. Alternatively, [PPh 4 ] 2 [Cu(SPh) 3 ] [18] was treated with [Cu(CH 3 CN) 4 ]ClO 4 ·2H 2 O in boiling acetonitrile to synthesize the same compound, but the yield of the product in these procedures was not reported.…”

“…In another procedure, the use of Cu I as the source material was made and this was treated with KSPh in acetonitrile and the [PPh 4 ] 2 salt of 4 [18] was isolated. Alternatively, [PPh 4 ] 2 [Cu(SPh) 3 ] [18] was treated with [Cu(CH 3 CN) 4 ]ClO 4 ·2H 2 O in boiling acetonitrile to synthesize the same compound, but the yield of the product in these procedures was not reported. In the present work, our intention was to understand the solubility of the Cu-thiolate polymer in the form of isolable discrete cluster anions as quaternary ammonium ion salts in the presence or absence of an excess amount of thiolate ions.…”

“…Among the common Cu n clusters (n = 4, [12] 6, [8,9] 7 [13] and 8 [10,11] ) known to be present in Cu-MT, the varied ligation number of the thiolate ion (CysS m , m = 4 to 11) contributes to the diverse stoichiometry that one can anticipate in Cu-MT clusters. Accordingly, many examples of monodentate thiolatocopper(I) clusters have been reported so far by X-ray crystallography [14][15][16] [CuS 2 , [17] CuS 3 , [18,19] Cu 2 S 2 , [20] Cu 3 S 3 , [21] Cu 4 S 4 , [22] Cu 4 S 6 , [18,[23][24][25][26] Cu 5 S 6 , [27,28] Cu 5 S 7 , [29] Cu 6 S 4 (in this work) Cu 7 S 8 , [30] Cu 8 S 8 [31] and Cu 12 S 12 [32] ]. 6 ] (4).…”

Metal-selenolate chemistry: stereochemistry of adamantane-type clusters of formula [(μ-SePh)6(MSePh)4]2− (M = Zn and Cd)

“…Before use, solvents were dried over 3 A Molec-20 such compounds have been characterized by X-ray ular Sieves and sparged with Ar(g). The salt (Me4N),[Cd4(SePh),o], structure analyses (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20). By contrast, the structural chem-3, was synthesized as reported earlier (22), istry of analogous metal-selenolates is essentially undeveloped.…”