Preparation of Hydrido η⁶-Hexamethylbenzene Complexes of Ruthenium(II) Containing Various Tertiary Phosphines. Displacement of Coordinated Triphenylarsine or Triphenylstibine From RuHCl (η⁶-C₆Me₆)L (L = AsPh₃, SbPh₃)

Abstract

Twelve new complexes in the series RuHCl (η⁶-C₆Me₆)L [L = PBu^t₂Me (5), PBu^t₂Et (6), PBu^t₂Pr (7), PMe₃ (8), PMe₂Ph (9), PMePh₂ (10), PEtPh₂ (ll), PPh₂Pr (12), P( OPh )₃, (13), P(OMe )₃ (14), PEt₃ (15), or PPh₂(C₆H₄Me-o) (16)] have been prepared by one of three methods: 1, heating [RuCl₂(η⁶-C₆Me₆)]₂ with an excess of L and of anhydrous Na₂CO₃ in propan-2-ol (5)-(7); 2, heating pre-formed RuCl₂(η⁶-C₆Me₆)L with an excess of Na₂CO₃ in propan-2-ol (8), (9), (11); 3, displacement of AsPh₃ or SbPh₃ by L from RuHCl (η⁶-C₆Me₆₎ L (L= AsPh₃, SbPh₃) (10)-(16). The new dihydrido complexes RuH₂(η⁶-C₆Me₆)L (17)-(19) have been made by NaBH₄ reduction of either RuCl₂(η⁶C₆Me₆)L [L = PMe₂Ph (17), PBu^tMe₂ (18) or of RuHCl (η⁶ -C₆Me₆)L [L = Pbu^t₂Et (19)]. Under the conditions of method 2, RuCl₂(η⁶-C₆Me₆)(PPh₂(C₆H₄Me-o)) (4) undergoes deprotonation at the o- tolyl methyl group to give the cyclometallated complex RuCl (CH₂C₆H₄PPh₂-o)( η⁶-C₆Me₆) (20).