Selective transformation of carbonyl ligands to organic molecules
Three objectives of our studies on the catalytic hydrosilation of organo-transition metal acyl complexes have been attained. First, efficient catalysts and near optimal reaction conditions now supersede our previous procedures using (PPh{sub 3}){sub 3}RhCl. Manganese acyl compounds L(CO){sub 4}MnCOR (L = CO/R = Me, Ph; L = PPh{sub 3}, PEt{sub 3}/R = Me) as catalysts (0.1 to 10%) promote addition of R{prime}{sub 2}SiH{sub 2} (R{prime} = Et, Ph) and R{prime}{sub 3}SiH (R{prime}{sub 3} = Et{sub 3}, Me{sub 2}Ph) across FpCOR{double prime} (R{double prime} = Me, Ph), our test substrates. Second, diastereo-selective hydrosilylation ((PPh{sub 3}){sub 3}RhCl catalysis/R{prime}{sub 2}SiH{sub 2}) of chiral Fe and Ru acetyl complexes Cp(L)(CO)M-COCH{sub 3} (L = P(OMe){sub 3}, PEt{sub 3}, PPh{sub 3}) has been achieved. Studies in progress focus on comparing this diastereoselectivity with that observed in generating corresponding {alpha}-alkoxyethyl complexes from reduction of Cp(L)(CO)M = C(OEt)CH{sub 3}{sup +} and on minimizing the subsequent conversion of the resulting siloxyethyl complexes to their vinyl derivatives, Cp(L)(CO)M {minus} CH = CH{sub 2}. Third, coupling hydrosilylation and subsequent carbonylation steps has been achieved using (CO){sub 5}Mn acyl complexes. Satisfactory progress also is being made on the hydrosilylation (catalytic-potentially drastereoselective) then carbonylation of ({eta}{sup 5}-indenyl)Ru acetyl compounds, In(L)(CO)Ru--COCH{sub 3}.
- Research Organization:
- Rensselaer Polytechnic Inst., Troy, NY (USA). Dept. of Chemistry
- Sponsoring Organization:
- DOE/ER
- DOE Contract Number:
- FG02-86ER13617
- OSTI ID:
- 6716864
- Report Number(s):
- DOE/ER/13617-4; ON: DE90015387
- Country of Publication:
- United States
- Language:
- English
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Selective transformation of carbonyl ligands to organic molecules. Progress report, September 1, 1989--November 14, 1992
Selective transformation of carbonyl ligands to organic molecules
Related Subjects
400201* -- Chemical & Physicochemical Properties
CARBONYLATION
CARBONYLS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COBALT
COMPLEXES
DOCUMENT TYPES
ELEMENTS
HYDRIDES
HYDROGEN COMPOUNDS
IRON COMPLEXES
KINETICS
MANGANESE COMPOUNDS
METALS
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PLATINUM METALS
PROGRESS REPORT
REACTION KINETICS
RHODIUM
RUTHENIUM COMPLEXES
SILANES
SILICON COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS