Metal Carbonyl-Hydrosilane Reactions and Hydrosilation Catalysis

Cutler, A. R.

Rensselaer Polytechnic Institute

关键词: Chemical Reactions;    Catalytic Effects;    37 Inorganic, Organic, Physical And Analytical Chemistry;    Silanes;    Carbonyls;   

DOI  :  10.2172/833810
RP-ID  :  DOE/ER/14542
RP-ID  :  FG02-95ER14542
RP-ID  :  833810

美国|英语

来源: UNT Digital Library

【 摘 要 】

Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a siloxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Three relevant catalytic reactions are shown. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(C0){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as well as hydrosilation and deoxygenation of some metallocarboxylic acid derivatives. In every case studied, these Mn precatalysts are far more reactive or selective than traditional Rh(I) precatalysts.