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First Dinuclear Copper/Gallium Complexes: Supporting Cu0 and CuI Centres by Low‐Valent Organogallium Ligands
Authors:Timo Bollermann  Ganesan Prabusankar Dr  Christian Gemel Dr  Rüdiger?W Seidel Dr  Manuela Winter  Roland?A Fischer Prof?Dr
Institution:1. Inorganic Chemistry II—Organometallics & Materials, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44870 Bochum (Germany), Fax: (+49)?234‐321‐4174;2. Department of Analytical Chemistry, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44870 Bochum (Germany)
Abstract:The synthesis and structural characterisation of low‐valent dinuclear copper(I) and copper(0) complexes supported by organogallium ligands has been accomplished for the first time by the reductive coordination reaction of GaCp*] (Cp*=pentamethylcyclopentadienyl) and Ga(ddp)] (ddp=HC(CMeNC6H3‐2,6‐iPr2)2 2‐diisopropylphenylamino‐4‐diisopropylphenylimino‐2‐pentene) with readily available copper(II) and copper(I) precursors. The treatment of CuBr2 and Cu(OTf)2 (OTf=CF3SO3) with Ga(ddp)] under mild conditions resulted in elimination of Ga(L)2(ddp)] (L=Br, OTf) and afforded the novel gallium(I)/copper(I) compounds {(ddp)GaCu(L)}2] (L=Br ( 1 ), OTf ( 2 )). The single‐crystal X‐ray structure determinations of 1 and 2 reveal that these molecules are composed of {(ddp)GaCu(L)} dimeric units, with planar CuI? GaI four‐membered rings and short CuI???CuI distances, with 2 exhibiting the shortest CuI???CuI contact reported to date of 2.277(3) Å. The all‐gallium coordinated dinuclear Cu2(GaCp*)(μ‐GaCp*)3Ga(OTf)3] ( 3 ) is formed when Cu(OTf)2 is combined with GaCp*] instead of Ga(ddp)]. Notably, in the course of this redox reaction Lewis acidic Ga(OTf)3 is formed, which coordinates to one of the electron‐rich copper(0) centres. Compound 3 is suggested as the first case of a structurally characterised complex of copper(0). By changing the copper(II) to a copper(I) source, that is, Cu(cod)2]OTf] (cod=1,5‐cyclooctadiene), the salt Cu2(GaCp*)3(μ‐GaCp*)2]OTf]2 ( 4 ) is formed, the cationic part of which is related to previously described isoelectronic dinuclear d10 complexes of the type M2(GaCp*)5] (M=Pd, Pt).
Keywords:copper  gallium  Lewis acids  Lewis bases  ligand effects  metal–  metal interactions
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