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) (<5 min) ≫ (CO)5MnC(O)Ph
> (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 activity in transforming
acetone
to 3. In contrast,
(CO)4CoSiMe2Ph (10) or
Co2(CO)8 in the presence of the excess
HSiMe2Ph, with or without photochemical activation, were ineffective acetone
hydrosilation catalysts.
A reaction pathway is presented for the manganese
carbonyl-catalyzed hydrosilation of
ketones that involves coordinatively unsaturated manganese silyl
intermediates, (L)(CO)MnSiR‘‘3, as the active catalysts.
The silyl esters
Cp(PPh3)(NO)ReCO2SiR3
(2)
are produced from treatment of
Cp(PPh3)(NO)ReCOBF4
with the silanolates R3SiONa (R3Si
= PhMe2Si, Et3Si)
in CH2Cl2 (0 °C) or of
Cp(PPh3)(NO)ReCO2K with
R3SiCl in THF. Upon handling, 2 degraded to the
bimetallocarboxylates
Cp(PPh3)(NO)ReCO2Re(CO)(NO)(PPh3)(OSiR3) (3), one of which
(SiR3 = SiMe2Ph) was
characterized by X-ray crystallography as a
μ-η1(C(Re1)):η2(O,O‘(Re2)) bimetallocarboxylate.
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