Metal Carbonyl-Hydrosilane Reactions and Hydrosilation Catalysis.

Cutler, A. R.

Technical Information Center Oak Ridge Tennessee

关键词: Carbonyls;    Catalysis;    Chemical reactions;    Adducts;    Alcohols;   

RP-ID  :  DE2003805815

学科分类：工程和技术（综合）

美国|英语

来源: National Technical Reports 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. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(CO)(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(l) precatalysts. The reaction chemistry of the above and other Mn alkyl complexes with hydrosilanes was studied in order to probe catalysis mechanism(s).