Phosphine- and Metal Hydride-Induced Migratory Insertion in Molybdenum Carbonyl Alkyls

摘要

The acyl-forming reaction of PMePh sub 2 with CpMo(CO) sub 3 CH sub 3 (Cp = eta exp 5 -C sub 5 H sub 5 ) has been examined in a series of substituted tetrahydrofurans. Kinetic studies reveal two competing pathways in tetrahydrofuran (THF). Brief investigations of reactions with PEt sub 3 and P(OPh) sub 3 indicate operation according to similar mechanisms, with some alteration in rate constants. The reaction of CpMo(CO) sub 3 R (1; R = CH sub 3 , C sub 2 H sub 5 ) with CpMo(CO) sub 3 H (2), which produces RCHO, (CpMo(CO) sub 2 ) sub 2 , and (CpMo(CO) sub 3 ) sub 2 , occurs by way of two competing pathways. No hydrogen-dueterium kinetic isotope effect is observed on either k sub 4 or k sub 5 when CpMo(CO) sub 3 D is substituted for 2. (ERA citation 08:057462)