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(EC 6 X 5 )(CO)(P i Pr 3 ) 2 ] ( 2–4, 10, 11, 15–19 ) have been prepared from [MHCl(CO)(P i Pr 3 ) 2 ] and NaEC 6 X 5 in good to excellent yields. Whereas in 2, 3, 15, 16 and in all the hydrido(thiophenolate) complexes the EC 6 X 5 ligand is η 1 ‐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 O 2 to give stable 1:1 adducts 7, 8 and with CS 2 by insertion to yield [MH(η 2 ‐S 2 COC 6 X 5 )(CO)(P i Pr 3 ) 2 ] ( 5, 6 ). From 10, 11, 19 and CS 2 , the corresponding trithiocarbonate complexes 12, 13, 20 have been prepared. Treatment of 4 with Cl 2 leads to the formation of [OsCl(η 2 ‐OC 6 Cl 5 )(CO)(P i Pr 3 ) 2 ] ( 9 ) by cleavage of the Os–H bond.