Fünf‐ und sechsfach koordinierte Hydrido(phenolat)‐ und Hydrido(thiophenolat)‐Komplexe von Ruthenium und Osmium

Penta- and Hexacoordinate Hydrido(phenolate) and Hydrido(thiophenolate) Complexes of Ruthenium and Osmium The hydrido(phenolate)- and Hydrido(thiophenolate)ruthenium and -osmium complexes [MH(EC6X5)(CO)(PiPr3)2] (2–4, 10, 11, 15–19) have been prepared from [MHCl(CO)(PiPr3)2] and NaEC6X5 in good to excellent yields. Whereas in 2, 3, 15, 16 and in all the hydrido(thiophenolate) complexes the EC6X5 ligand is η1-bonded (by O or S), in 4 and 17 the pentachlorophenolate is coordinated in a bidentate mode. This is confirmed by the X-ray structural analysis of 4 which reveals a surprisingly short Os–Cl distance. The compounds 2 and 3 react with O2 to give stable 1:1 adducts 7, 8 and with CS2 by insertion to yield [MH(η2-S2COC6X5)(CO)(PiPr3)2] (5, 6). From 10, 11, 19 and CS2, the corresponding trithiocarbonate complexes 12, 13, 20 have been prepared. Treatment of 4 with Cl2 leads to the formation of [OsCl(η2-OC6Cl5)(CO)(PiPr3)2] (9) by cleavage of the Os–H bond.