Group IB organometallic Chemistry XXIII. Reaction of Ar4Cu2Li2 with RhI complexes; Synthesis of 2-[(dimethylamino)methyl] phenylrhodium dicarbon monoxide and electron-transfer induced selective formation of diarylketones ArC(O)Ar

Abstract

The 1/1 reaction of (2-Me{2}NCH{2}C{6}H{4}){4}M{2}Li{2} (M = Cu or Au) with (CO){2}ClRh-dimer affords (2-Me{2}NCH{2}C{6}H{4}M){n} and the novel 2-Me{2}NCH{2}C{6}H{4}Rh(CO){2}. In contrast, the reaction of (x-tolyl){4}M{2}Li{2} (x = 2, M = Cu or Au) under a CO atmosphere results in the formation of ditolyl ketone bitolyl in 69, 92 and 31, 4% yield, respectively. In the presence of TMED (x = 4, M = Cu) ditolyl ketone is formed exclusively. The reaction of (4-tolyl){4}Cu{2}Li{2} with (C{2}H{4}){2}ClRh-dimer under C{2}H{4} atmosphere gives 4, 4'-bitolyl, quantitatively.A reaction pathway is proposed which involves formation of [(CO){2}Rh(aryl){2}M]{n} (M = Cu or Au) as a key intermediate.