Abstract
The formation of the carbonyl complexes (S Ru, R C )-[Ru(η 5-C 5H 5)(CO)(prophos)]PF 6 ( 3a) (prophos = Ph 2PCH(CH 3) CH 2PPh 2) and ( R Ru, RC)-[Ru(CO)(η 5-C 5H 5)(prophos)]PF 6 ( 3b) by reaction of the corresponding chloro compounds 1a and 1b with carbon monoxide in the presence of NH 4PF 6 is stereospecific, and takes place with retention of configuration at the ruthenium atom. The carbonyls 3a and 3b are also stereospecifically formed by reaction of the vinylidene complexes ( S Ru, R C)-[Ru(η 5-C 5H 5)(CCHPh)(prophos)]PF 6 ( 2a) and ( R Ru, R C)-[Ru(CCHPh)(η 5-C 5H 5) (prophos)]PF 6 ( 2b) with molecular oxygen. The reaction of 3a with LiAlH 4 to give the methyl derivatives is stereospecific but that of 3b shows extensive epimerization as well as a low chemoselectivity. A similar difference in stereoselectivity for the two diasteromers 3a and 3b is also observed in the reaction with [N(C 2H 5) 4]OH.
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