leads to the dimeric salt [Fe2( C6H7·Ph2PCH2)2}(CO)6][BF4]2. The rate law, Rate =k[Fe][PR3], is observed for addition of a range of phosphines and phosphites to (1) and the related cations [Fe(C6H6OMe)(CO)3]+ and [Fe(C7H9)(CO)3]+. Rate and activation parameters indicate direct addition at the dienyl rings. The marked dependence of k on the basicity of phosphorus nucleophiles suggests significant
叔膦和
亚磷酸酯与二烯基络合物如[Fe(C 6 H 7)(CO)3 ] [BF 4 ](1)的反应为[Fe(C 6 H 7 · PR 3)(CO)3 ] [BF 4 ](R = Ph,
对甲苯基,Bu n,OPh或OBu n)。与1,2-双(
二苯基膦基)
乙烷的类似反应产生二聚盐[Fe 2 (C 6 H 7 ·Ph 2 PCH 2)2 }(CO)6 ] [BF4 ] 2。率法,速率= ķ的[Fe] [PR 3 ],观察到用于加成的范围膦和
亚磷酸酯的与(1)和相关的阳离子的[Fe(C 6 H ^ 6 OME)(CO) 3 ] +和[Fe(C 7 H 9)(CO) 3 ] +。速率和活化参数表明在二烯基环上直接加成。k对
磷亲核试剂碱性的显着依赖性表明在加合物形成的过渡态中会形成大量键。