Reactions of iminophosphanes with chlorotris(triphenylphosphine)rhodium(I): generation and NMR identification of the first iminophosphanerhodium(I) and iminophosphanerhodium(III) complexes

摘要

Iminophosphanes [RO-P=NAr] (R = Me, 2-MeC6H4; Ar = 2,4,6-Bu'3C6H2) 1a,b react with RhClL3 (L = Ph3P) via ligand exchange to give KP-iminophosphane complexes of rhodium(i) [RhCl(MeOP=NAr)2L] 2 and [PhCl(2-MeC6H4OP=NAr)L2] 3. Under analogous conditions, P-halogenoiminophosphanes [X-P=NAr] (X = Cl, Br, I) 3a–c undergo a facile oxidative addition of the P-X bond, forming five-coordinate iminophosphanerhodium(III) complexes of composition [L2Cl(X)Rh(σ-P=BAr)] 5.