Mononuclear and heterodinuclear transition metal complexes of functionalized phosphinesCrystal and molecular structures of [Mo(CO)5(RPC6H4OCH2OCH3-o)] (R=Ph, C6H4OCH2OCH3-o), [Ru(Ph2PC6H4O-o)3], [Pd(Ph2PC6H4O-o)2] and [PdCl(Ph2PC6H4O-o)(Ph2PC6H4OH-o)

Abstract

Transition metal complexes of phosphine ethers (Ph2PC6H4OCH2OCH3-o and PhP(C6H4OCH2OCH3-o)2) and phosphinophenol, Ph2PC6H4OH-o are described. Phosphine ethers react with Group 6 metal carbonyls to form complexes of the type [M(CO)4L2] and [M(CO)5L] (M = Mo, Cr, W). The reaction of Ph2PC6H4OCH2OCH3-o with RuCl3 · 3H2O gave ruthenium(III) complex, [Ru(Ph2PC6H4O-o)3] through the elimination of CH3OCH2Cl whereas the reaction with CpRu(PPh3)2Cl resulted in the formation of [CpRu(Ph2PC6H4O-o)PPh3]. Treatment of Ph2PC6H4OCH2OCH3-o with rhodium(I) derivatives resulted in the formation of complexes with the phosphine exhibiting both mono- and bidentate modes of coordination involving the phosphorus center and the phenolic oxygen. The reaction of Ph2PC6H4OCH2OCH3-o with [PdCl2(COD)] led to the isolation of two mononuclear complexes, [PdCl(Ph2PC6H4O-o)(Ph2PC6H4OH-o)] cocrystallized with phosphonium salt, [Ph2P(CH2OCH3)C6H4OH-o]Cl and [Pd(Ph2PC6H4O-o)2] as confirmed by X-ray diffraction studies. The former shows extensive hydrogen bonding interactions between the complex and the phosphonium salt. The metalloligand, Cp2Zr(OC6H4PPh2-o)2 obtained by the reaction of Cp2ZrCl2 with Ph2PC6H4OH-o form heterobimetallic complexes with Mo(0), Re(I) and Ni(0) carbonyl derivatives. The reactions of Cp2Zr(OC6H4PPh2-o)2 with metal halides such as M(COD)Cl2 (M = Pd, Pt) and CpRuCl(PPh3)2 afforded metallacycles, [M(Ph2PC6H4O-o)2] and [CpRu(PPh2C6H4OH-o)(PPh2C6H4O-o)], respectively via transmetallation.