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Isolated monomeric and dimeric mixed diorganocuprates based on the size-controllable bulky "rind" ligands
Mikinao Ito1, Daisuke Hashizume, Takeo Fukunaga
1Functional Elemento-Organic Chemistry Unit, RIKEN Advanced Science Institute, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Abstract:
Isolable mixed diorganocopper(I) complexes have been synthesized and structurally characterized by introducing a variety of bulky "Rind" groups based on a fused-ring octa-R-substituted s-hydrindacene skeleton. Treatment of RindLi with CuBr produced organobromocuprate dimers [Cu(Rind)/CuBr](2) or monomers Li[Cu(Rind)Br], depending on the steric bulkiness of the Rind ligands. Subsequent substitution of the bromine atoms in these complexes by lithium trimethylsilylacetylide gave dimeric and monomeric aryl(alkynyl)copper(I) complexes A and B, respectively. Complex B is the first isolable mixed diorganocuprate monomer formulated as LiCuRR' and was found to selectively undergo oxidative cross-coupling of two different organic groups on copper.
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