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Copper( I ) Complexes with a Cu 4 S 6 ‐ and CuS 4 ‐Type Core Obtained from the Reaction of Copper(0) with HN(SPPh 2 ) 2 ·I 2
Author(s) -
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.,
Verani Gaetano
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500639
Subject(s) - chemistry , copper , protonation , crystallography , adduct , metal , nuclear magnetic resonance spectroscopy , chelation , sulfur , inorganic chemistry , stereochemistry , ion , organic chemistry
Abstract The copper( I ) compounds [Cu I 4 (L) 3 ]I 3 ( 1 ) and [Cu I (HL) 2 ]I 3 · CH 3 CN ( 2 ) [HL = HN(SPPh 2 ) 2 ] have been obtained from the reaction of the adduct HL · I 2 with copper(0) powder in diethyl ether solution. Compound 1 contains a tetrahedron of Cu atoms with three anionic L ligands coordinated to the coppers through the sulfur atoms to build a Cu 4 S 6 core. The mean Cu–Cu and Cu–S bond lengths related to the Cu 4 S 6 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) 3 ] + 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 CuS 4 core. The 31 P 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 °C to an A 2 spin system at 40 °C. The reaction of [Cu 4 (L) 3 ] + with HI, monitored by 31 P NMR spectroscopy, leads to the protonation of the complexed ligands at the Cu 4 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 [Cu 4 (L) 3 ] + .(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)