Journal of Organometallic Chemistry p. 73 - 93 (1985)
Update date:2022-08-04
Topics:
Werner
Gotzig
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)nL4-n]PF6 are obtained on oxidation of MCl2(PMe3)nL4-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)nL4-n.
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Doi:10.1016/S0040-4039(00)98606-4
(1985)Doi:10.1139/v85-464
(1985)Doi:10.1016/S0040-4039(00)93566-4
(1991)Doi:10.1007/BF00515059
(1985)Doi:10.1246/cl.1985.585
(1985)Doi:10.1002/anie.201712775
(2018)
