Pd_2X_2(dpm)_2(X=Cl^-,Br^-,I^-)与H_2S反应的低温NMR研究

Low Temperature NMR Study on the Reactions Between Pd_2X_2(dpm)_2(X = Cl^- , Br^-, I^-) and H_2S

采用低温NMR技术考察了配合物Pd_2X_2(dpm)_2(X=Cl^-,Br^-,I^-;dpm=Ph_2PCH_2PPh_2)与H_2S在CD_2Cl_2溶液中的反应,对反应中间体进行了详细的表征.结果表明,反应首先由H_2S对Pd_2X_2(dpm)_2的Pd-Pd键氧化加成,形成相应的带有Pd-H和Pd-SH的中间体,该中间体随后脱去H_2并转化为相应的S^(2-)桥联的配合物Pd_2X_2(dpm)_2(μ-S).

Low temperature NMR technique was used to investigate the reactions of H2S and Pd2X2 (dpm)2(X = Cl-, Br-, I- ; dpm = Ph2PCH2PPh2) in CD2Cl2. The detail NMR data for the reaction intermediate are presented which show that the reactions form the corresponding bridged-sulfide complexes via oxidative-addition of H2S across the Pd-Pd bond of Pd2X2(dpm)2 to give a hydrido(mercapto)intermediate, which subsequently liberates H2 to give Pd2X2(dpm)2(μ-S) species.