Metal carbonyl-hydrosilane reactions and hydrosilation catalysis. Final report for period May 1, 1995 - August 14, 1999

Cutler, Alan R.

Rensselaer Polytechnic Institute

关键词: Aldehydes;    Halides;    Ketones;    37 Inorganic, Organic, Physical And Analytical Chemistry;    Manganese;   

DOI  :  10.2172/805815
RP-ID  :  DOE/ER14542
RP-ID  :  FG02-95ER14542
RP-ID  :  805815

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 doxy 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). Thus, Mn(CO){sub 5} methyl, benzyl, acetyl, and benzoyl (4 p-substituents) complexes reacted with hydrosilines by four different mechanisms, which were established. A noteworthy development was that the methyl and benzoyl complexes gave moderate yields of a new ({eta}{sup 2}-Si-H) silane adduct (CO){sub 4}Mn(SiMe{sub 2}Ph)(H-SiMe{sub 2}Ph), which is stable in the presence of excess silane. This silane adduct promotes all three catalytic reactions; its extraordinary activity and potential selectivity are under study.