L′2 = cod) is reported. Complex 1a reacts with CO to form 1c (L = L′ = CO) via the intermediate 1b (L2 = cod, L′ = CO). 1a and 1c do not incorporate 13CO2 or D2 in the formate moiety and are poor catalysts for CO2 hydrogenation to formic acid. Reaction of 1a with the chelating phosphanes R2P(CH2)2PR2 () 3a-c leads to replacement of the diolefin ligand and cleavage of the dimeric structure under formation
的X射线晶体结构分析[(L 2)的Rh(μ - κ 2 O,O'HCO 2)2的Rh(L' 2)] 1A(L 2 = L' 2 = COD)被报告。配合物1a通过中间体1b与CO反应生成1c(L = L'= CO)(L 2 = cod,L'= CO)。1a和1c在
甲酸酯部分中没有掺入13个CO 2或D 2,并且是将CO 2加氢成
甲酸的不良催化剂。的反应在图1a中用螯合膦R 2 P(CH 2)2 PR 2()3a-c导致二烯烃
配体的置换和在单体配合物[(3a-c)2 Rh] [HCO 2的形成下的二聚结构的裂解。] 4a-c。分离出4a,产率高达78%,并且检测到复合物6a为副产物。使用双齿
配体Ph 2 P(CH 2)3 PPh 2 3d仅在相同的反应条件下形成6型配合物或单齿
配体PAr 3 3e-f。为复合物形成的一种可能的机制4,5和6讨论涉及从HCO
氢化物转移2 -
配体与
铑并随后协调鳕鱼。