Abstract
Reaction of an alkenyl acetate, [CH 3 CO 2 CR=CH 2 ] (R=CH 3 , C 6 H 5 ), with triethylsilane in the presence of either the closo-rhodacarborane [closo-3,3-(PPh 3 ) 2 -3-H-3,1,2-RhC 2 B 9 H 11 ] (I) or the exo-nido-rhodacarborane [exo-nido-(PPh 3 ) 2 Rh-7,8-(μ(CH 2 ) 3 )7,8-C 2 B 9 H 10 ] (II) as catalyst precursors in CH 2 Cl 2 at 40 o C for 42 h yielded triethylsilyl acetate and the alkene derived from the alkenyl acetate rather than the hydrosilylation product. The closo complex I was shown to be a superior catalyst precursor, giving over 80 turnovers, which corresponds to 80% conversion of alkenyl acetate to trialkylsilyl acetate under experimental conditions. Under mild conditions, tris(triphenylphosphine) chlororhodium, [(PPh 3 ) 3 RhCl] (IV), was found to catalyze the hydrosilanolysis as well as the hydrosilylation of isopropenyl acetate. The mechanisms of the hydrosilanolysis and related reactions of alkenyl acetates are discussed
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