Rearrangements of phosphinoimines to phosphine-imines in ruthenium chelate complexes

Thermal reaction of 1:1 mixtures of the RuCl(2)(PPh(3))(3) and phosphinoimine R(2)PN=CPh(2) (R = Ph, iPr, Me) at 140 °C results in isolation of the dimeric species [RuCl(μ-Cl)(PPh(3))(C(6)H(4)(PPh(2))C(Ph)NH)](2) (R = Ph 1, iPr 2, Me 3) containing phosphine-imine chelating ligands. Subsequent reaction of 1 and 3 with one equivalent of pyridine at room temperature give RuCl(2)(PPh(3))(py)(C(6)H(4)(PR(2))C(Ph)NH) (R = Ph 4, Me 5). Excess pyridine reacts with 2 to give a mixture of the cis and trans-isomers of RuCl(2)(py)(2)(C(6)H(4)(PiPr(2))C(Ph)NH) 6 and 7 respectively. Treatment of 5 with excess PPh(3) affords RuCl(2)(PPh(3))(2)(C(6)H(4)(PMe(2))C(Ph)NH) 8. Aspects of the mechanism of the thermal rearrangements of the phosphinoimine to the phosphine-imine ligands are considered and the isolation of RuCl(2)(Ph(2)PN=CPh(2))(SIMes)(CHPh) 9 and RuCl(2)(PPh(3))(2)(HN=C(Ph)C(6)H(4)) 10 provide support for a proposed mechanism involving a intermediate containing a Ru-bound metallated aryl-imine fragment.