Reactions of Iminophosphanes with Chlorotris(triphenylphosphine)rhodium(I): Generation and NMR Identification of the First Iminophosphanerhodium(I) and Iminophosphanerhodium(III) Complexes

Iminophosphanes [RO-P=NAr] (R = Me, 2-MeC₆H₄; Ar = 2,4,6-Bu^t₃C₆H₂) 1a,b react with RhCIL₃ (L = Ph₃P) via ligand exchange to give _KP-iminophosphane complexes of rhodium(i) [RhCI(MeOP=NAr)₂L] 2 and [PhCI(2-MeC₆H₄OP=NAr)L₂] 3. Under analogous conditions, P-halogenoiminophosphanes [X-P=NAr] (X = CI, Br, I) 3a–c undergo a facile oxidative addition of the P—X bond, forming five-coordinate iminophosphanerhodium(iii) complexes of composition [L₂CI(X)Rh(<σ-P=BAr)] 5.