Abstract
A series of η1-α-phosphinocarbene complexes of manganese, Cp(CO)2Mn═C(R)PR′R′′ (3; 3a: R = Ph, R′ = H, R′′ = Mes; 3b: R = Me, R′ = H, R′′ = Mes; 3c: R = Ph, R′ = R′′ = Ph; 3d: R = Ph, R′ = R′′ = N(i-Pr)2; 3e: R = Ph, R′ = Me, R′′ = Mes), was generated at low temperature upon nucleophilic addition of the primary phosphine H2PMes and secondary phosphines HPPh2, HP(N(i-Pr)2)2, or (±)-HPMeMes to the cationic carbyne complexes Cp(CO)2Mn+≡C−R ([1]+; [1a]+: R = Ph; [1b]+: R = Me), followed by deprotonation of the resulting α-phosphoniocarbene intermediates Cp(CO)2Mn═C(R)P+(H)R′R′′ ([2a−e]+). The η1-α-phosphinocarbene complexes 3c−e derived from secondary phosphines were found to be highly thermolabile, giving upon intramolecular CO insertion the η3-phosphinoketene complexes Cp(CO)Mn(η3-C(O)C(Ph)PR′R′′) (4c: R′ = R′′ = Ph, 4d: i-Pr2N; RR/SS-4e: R′ = Me, R′′ = Mes) in 80−95% yield. The η1-α-phosphinocarbene complexes 3a,b, bearing a mesityl substituent, were isolated in 57−65% yield. The availability of the phosph...
Published Version
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call