199176-19-7Relevant academic research and scientific papers
Five-coordinate complexes MHCl(CO)(PiPr3)2 (M = Os, Ru) as precursors for the preparation of new hydrido-and alkenyl-metallothiol and monothio-β-diketonato derivatives
Buil, María L.,Elipe, Sergio,Esteruelas, Miguel A.,O?ate, Enrique,Peinado, Elena,Ruiz, Natividad
, p. 5748 - 5755 (1997)
The five-coordinate complexes MHCl(CO)(PiPr3)2 (M = Os (1), Ru (2)) react with NaSH to give the unsaturated hydrido-metallothiol derivatives MH(SH)(CO)(PiPr3)2 (M = Os (3), Ru (4)). Complexes 3 and 4 react with CO to afford the cis-dicarbonyl compounds MH(SH)-(CO)2(PiPr3)2 (M = Os (5), Ru (6)). Similarly, the reaction of 3 with P(OMe)3 leads to OsH-(SH)(CO){P(OMe)3}(PiPr3)2 (7). Treatment of 3 with 1 equiv of acetylenedicarboxylic methyl ester affords OsH{SC(CO2CH3)CHC(OCH3)O}(CO)(P iPr3)2 (8), which is the result of the trans addition of the S-H bond of 3 to the carbon-carbon triple bond of the alkyne. The structure of 8 was determined by X-ray investigation. The geometry of the complex can be rationalized as a distorted octahedron with the two phosphorus atoms of the triisopropylphosphine ligands occupying apical positions. The equatorial plane is formed by the bidentate ligand, which acts with a bite angle of 89.49(12)°, the hydrido ligand trans-disposed to the oxygen atom, and the carbonyl group trans-disposed to the sulfur atom. Acetylenedicarboxylic methyl ester also reacts with 4 by insertion of the carbon-carbon triple bond into the S-H bond. However, in the resulting monothio-β-diketonato derivative RuH{SC(CO2CH3)CHC-(OCH3)O}(CO)(P iPr3)2 (9) the hydrido ligand lies trans to the sulfur atom. In solution, complex 9 isomerizes into 10, containing the hydrido ligand trans-disposed to the oxygen atom of the chelate group. The stereochemistry of 10 was corroborated by X-ray investigation. The geometry of 10 is the same as that of 8, and the structural parameters of both molecules are statistically identical. Phenylacetylene and methylpropiolate, in contrast to acetylene-dicarboxylic methyl ester, react with 3 and 4 by insertion of the carbon-carbon triple bonds into the M-H bonds to give the unsaturated alkenyl-metallothiol complexes M{(CE)-CH=CHPh}(SH)(CO)(PiPr3)2 (M = Os (11), Ru (12)) and Ru{(CE)-CH=CHCO2CH3}(SH)(CO)(Pi-Pr 3)2 (13).
