Reactions of Metal-Metal-Bonded Binuclear Complexes

点击翻译按钮获取中文摘要

1. Reactions of M <(acac)_2> (M=Pd,Pt) with dppm(= <Ph_2> <PCH_2> <PPh_2> ) to from M <(dppm-H)_2> (dppm-H=a deprotonated dppm anion) and methylation of the carbanions in Pt <(dppm-H)_2> with MeI have been studied, and both the reaction schemes were elucidated with the aim of <^1H> , <^(13)C> , or <^(31)P> NMR spectroscopy.2. Reactions of <[Pd(dppm)_2]^(2+)> with <[CpMo(CO)_3]^-> as a nucleophile was examined to obtain a certain heterobimetallic complex and the desired complex [ <(CO)_3> Mo <((mu)-dppm)_2> -PdCp] ( <PF_6> ) was synthesized and characterized. 3. Photochemical reactions of <[CpMo(CO)_3]_2> with <NO(_2^-)> or dark reactions of <[CpMo(CO)_2]_2> with <NO(_2^-)> and <NO(_3^-)> have been elucidated to give the mononuclear complex [CpMo <(CO)_2> (NO)], and the reaction mechanism was also proposed.4. The nucleophilic attak of <[CpMo(CO)_3^-> at the benzyl carbons of <alpha> , <alpha> ' -dibromo-o, m, p-xylene was found to afford <mu> -xylylene complexes which react with <PMe_2> Ph to give acyl complexes. It was revealed that photo-irradiation of the <mu> -xylylene complexes induce homolytic cleavage of the Mo-C bond.5. The redox behavior of <[Rh(C_5Me_5)Me]_2> <(mu)-CH_2)_2> were examined by cyclic voltammetry and the presence of three oxidation waves were recognized. A possible scheme on the oxidation was proposed based on the following experimental data: controlled potential electrolysis, analysis of the evolved gases, and ESR measurement of the electrolyzed solution.