Copper(I) complexes with a Cu4S6- and CuS4-type core obtained from the reaction of copper(0) with HN(SPPh2)(2)•I-2
Aragoni, M. Carla, Arca, Massimiliano, Carrea, M. Bonaria, Demartin, Francesco, Devillanova, Francesco A., Garau, Alessandra, Hursthouse, Michael B., Huth, Susanne L., Isaia, Francesco, Lippolis, Vito, Ogilvie, Helen R. and Verani, Gaetano (2006) Copper(I) complexes with a Cu4S6- and CuS4-type core obtained from the reaction of copper(0) with HN(SPPh2)(2)•I-2. European Journal of Inorganic Chemistry, (1), 200-206. (doi:10.1002/ejic.200500639).
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The copper(I) compounds [CU4I(L)(3)]I-3 (1) and [Cu-I(HL)(2)]-I-3•CH3CN (2) [HL = HN(SPPh2)(2)] have been obtained from the reaction of the adduct (HLI2)-I-. with copper(O) powder in diethyl ether solution. Compound I contains a tetrahedron of Cu atoms with three anionic L ligands coordinated to the coppers through the sulfur atoms to build a CU4S6 core. The mean Cu-Cu and Cu-S bond lengths related to the CU4S6 core in copper-loaded transcription factors CuAce1 and CuMac1, and in the model compound [Cu-4(SPh)(6)](2-), have been compared with those of the [Cu-4(L)(3)](+) cation, and the geometric volumes of the Cu-4 cores have been evaluated. The results suggest that the cation [Cu-4(L)31' is a possible structural model compound for the metal site in Ace1 and Mac1 transcription factors. In compound 2, two neutral HL ligands bind a Cu-I ion in an S,S'-isobidentate chelating fashion to form a slightly distorted tetrahedral CuS4 core. The P-31 NMR spectroscopic data of compound 1 are consistent with the maintenance of its structure in solution. Moreover, phosphorus variable-temperature measurements indicate a change from a two-spin coupled AB system at 0 degrees C to an A(2) spin system at 40 degrees C. The reaction of [Cu-4(L)(3)](+) with HI, monitored by P-31 NMR spectroscopy, leads to the protonation of the complexed ligands at the CU4 core and formation of the cation [Cu-4(HL)(3)](4+). The protonation reaction is reversible: increasing the amount of organic base 1,8-bis(dimethylamino)naphthalene (DMAN) regenerates the starting cation [CU4(L)(3)](+). (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).
|Keywords:||cluster compounds, copper, coordination chemistry, phosphanes, s ligands cuprous-thiolate clusters, crystal-structure, tetraphenyldithioimidodiphosphinic acid, derivatives, adduct, model|
|Subjects:||Q Science > QD Chemistry|
|Divisions:||University Structure - Pre August 2011 > School of Chemistry
|Date Deposited:||28 Feb 2007|
|Last Modified:||01 Jun 2011 14:32|
|Contributors:||Aragoni, M. Carla (Author)
Arca, Massimiliano (Author)
Carrea, M. Bonaria (Author)
Demartin, Francesco (Author)
Devillanova, Francesco A. (Author)
Garau, Alessandra (Author)
Hursthouse, Michael B. (Author)
Huth, Susanne L. (Author)
Isaia, Francesco (Author)
Lippolis, Vito (Author)
Ogilvie, Helen R. (Author)
Verani, Gaetano (Author)
|Contact Email Address:||M.B.Hursthouse@soton.ac.uk|
|RDF:||RDF+N-Triples, RDF+N3, RDF+XML, Browse.|
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