95858-32-5Relevant articles and documents
REACTIONS AT THE RHODIUM VERTEX OF ISOMERIC closo-BIS(TRIPHENYLPHOSPHINE)HYDRIDORHODACARBORANES, ALKENYL ACETATE CLEAVAGE AND SUBSEQUENT REACTIONS
King, R. E.,Busby, D. C.,Hawthorne, M. F.
, p. 103 - 114 (2007/10/02)
The isomeric hydridophosphinorhodacarboranerhodium(III) clusters, (1a); (1b); and (1c) react with isopropenyl acetate and vinylacetate under mild conditions to give ester C-O bond scission, expulssion of alkene, and formation of bidentate or monodentate acetate complexes of the form (PPh3))(η2-CH3COO)RhC2B9H11 or (PPh3)2(η1-CH3COO)RhC2B9H11.These acetate complexes react readily with hydrogen to regenerate the parent compounds.A very stable alkyl complex through the carbonyl oxygen could be isolated from the reaction of 1b with vinyl acetate at lower temperatures, whereas the reaction of 1a with either isopropenyl acetate or vinyl acetate at higher temperatures led to the formation of an ortho-metallated complex whose crystal structure is reported.When allyl acetate was employed as substrate, complexes of the form (PPh3)(η3C3H5)RhC2B9H11 resulted with concomitant elimination of acetic acid.The relevance of the novel compounds reported here to the catalytic hydrogenolysis of alkenyl acetates using 1a-1c as catalyst precursors is discussed.
