ALKYL- UND ARYLKOMPLEXE DES IRIDIUMS UND RHODIUMS. XV. PHOSPHONIT- UND PHOSPHINITINDUZIERTE CO-INSERTIONS- UND C-H-ADDITIONSREAKTIONEN ortho-METHYLSUBSTITUIERTER IRIDIUMARYLE. REVERSIBLE CH3-METALLIERUNG IM PHOSPHINITKOMPLEX

Article abstract of DOI:10.1016/S0022-328X(00)99504-4

The synthesis of a series of cyclometallated hydrido-iridium(III) compounds fac- (Ar = C6H4: R = R' = OMe.Ar = C6H2Me2-4,6:R = OMe, OEt, Ph; R' = OMe, OEt) from iridium(I) aryls Ir(CO)(PPh3)2 and phosphonites or phosphinites is reported.As a result of a reversible methyl-to-metal hydrogen transfer the tris(phosphinite) complex exists in solution in an equilibrium with Ir(CO)(Ph2POMe)2 and Ph2POMe.The demetallated iridium(I) compound predominates in this equilibrium which may be shifted in favour of the metallacyclic component by addition of excess phosphinite.