Article abstract of DOI:10.1016/0022-328X(85)80013-9

The complexes trans-MCl₂(PMe₃)₄ (M = Ru, Os) react with CO and P(OMe)₃ to give the mono- and disubstituted derivatives trans,mer-MCl₂(PMe₃)₃L (L = CO, P(OMe)₃) and all-trans-MCl₂(PMe₃)₂[P(OMe)₃]₂, respectively. On reaction of trans-RuCl₂[P(OMe)₃]₄ with CO and PMe₃, the compounds trans,mer-RuCl₂[P(OMe)₃]₃(CO) and trans,cis,cis-RuCl₂(PMe₃)₂[P(OMe)₃]₂ are synthesized. The reduction of MCl₂(PMe₃)₂[P(OMe)₃]₂ with Na/Hg in benzene or toluene via {M(PMe₃)₂[P(OMe)₃]₂} as an intermediate leads to subsequent intermolecular addition of the arene and to the aryl(hydrido)metal complexes cis,trans,cis-MH(C₆H₅)(PMe₃)₂[P(OMe)₃]₂ (M = Ru, Os) and MH(C₆H₄CH₃)(PMe₃)₂[P(OMe)₃)₂ (M = Os). For M = Ru, in the presence of P(OMe)₃, the ruthenium(0) compound Ru(PMe₃)₂(P(OMe)₃]₃ is formed. The hydrido(phenyl) complexes react with equimolar amounts of Br₂ or I₂ by elimination of benzene to produce the dihalogenometal compounds cis,trans,cis-MX₂(PMe₃)₂[P(OMe)₃]₂. The reaction of trans-RuCl₂(PMe₃)₄ with Na/Hg in the presence of PPh₃ leads to the ortho-metallated complex fac-RuH(η²-C₆H₄PPh₂)(PMe₃)₃, which reacts with CH₃I, CS₂, COS and HCl to give the compounds mer-RuI(η²-C₆H₄PPh₂)(PMe₃)₃, fac-Ru(SCHS)(η²-C₆H₄PPh₂)(PMe₃)₃, fac-Ru(S₂CO)(CO)(PMe₃)₃ and RuCl₂(PMe₃)₃, respectively. The paramagnetic 17-electron complexes [MCl₂(PMe₃)_nL_4-n]PF₆ are obtained on oxidation of MCl₂(PMe₃)_nL_4-n with AgPF₆. Their UV spectra exhibit a characteristic CT band. [RuCl₂(PMe₃)₄]PF₆ and [OsCl₂(PMe₃)₄]PF₆ react with CO and P(OMe)₃ by reduction to form the corresponding ruthenium(II) and osmium(II) compounds MCl₂(PMe₃)_nL_4-n.