Insertion of a Nontrigonal Phosphorus Ligand into a Transition Metal-Hydride: Direct Access to a Metallohydrophosphorane

摘要

The synthesis and reactivity of an NPN-chelating ligand containing a nontrigonal phosphorous triamide center (L1 = P(N(o -N(2-pyridyl)C_(6)H_(4))_(2)) is reported. Metalation of L1 with RuCl_(2)(PPh_(3))_(3) gives RuCl_(2)(PPh_(3))(L1 ) (2 ). By contrast, metalation of L1 with RuHCl(CO)(PPh_(3))_(3) yields RuCl(CO)(PPh_(3))(L1 ~(H)) (3 ), a chelated 10-P-5 ruthenahydridophosphorane, via net insertion into the Ru–H bond. Hydride abstraction from 3 with Ph_(3)CPF_(6) gives [RuCl(CO)(PPh_(3))(L1 )]PF_(6) (4 ); reaction of 4 with NaBH_(4) returns 3 .