Abstract
Manganese carbonyl complexes catalyze the hydrosilation of ketones with PhMe2SiH and Ph2SiH2 in C6D6 solutions. Efficacy of the manganese carbonyl precatalysts (2.4 mol %) toward acetone hydrosilation with 1.1 equiv of PhMe2SiH to give (CH3)2CH(OSiMe2Ph) (3) varied: (PPh3)(CO)4MnC(O)CH3 (1) ( (CO)5MnC(O)CH3 > (CO)5MnCH3 > (CO)5MnBr (6.0 h) ≫ Mn2(CO)10 ≈ (PPh3)(CO)4MnBr ≈ (CO)5MnSiMe2Ph (2). A turnover frequency of 27 min-1 was measured for catalysis using 1% 1; rapid catalysis was possible with 0.1% 1 in the absence of solvent. As a precatalyst, 1 is much more reactive than Rh(PPh3)3Cl for the PhMe2SiH hydrosilation of acetone, acetophenone, and cyclohexanone; both catalysts exhibit similar reactivity with Ph2SiH2. With 1 as the precatalyst, isolated yields of the alkoxydimethylphenylsilanes exceeded 90%, with no evidence of competing dehydrogenative silation to yield vinyl silyl ethers. Photochemical activation of (CO)5MnSiMe2Ph (2) affords moderate hydrosilation catalytic activ...
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