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 = PBut2Me (5), PBut2Et (6), PBut2Pr (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), PButMe2 (18) or of RuHCl (η6 -C6Me6)L [L = Pbut2Et (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).