Selective transformation of carbonyl ligands to organic molecules: Progress report for period September 1, 1982-August 31, 1983
Organometallic complexes containing C/sub 1/ alkoxycarbonyl and C/sub 2/ carboalkoxymethyl ligands derived from terminally bound CO were synthesized in order to delineate those coordinated ligand reactions and their intermediates that are viable for CO hydrogenation. The metalloester FpCO/sub 2/CH/sub 3/, derived from FpCO/sup +/ of from Fp/sub 2/Mg/CO/sub 2/, serves as the common template in converting either CO or CO/sub 2/ into the C/sub 1/ alkyl ligand on FpCH/sub 2/OCH/sub 3/; Fp = (eta-C/sub 5/H/sub 5/)Fe(CO)/sub 2/. First the activated ester FpC(OCH/sub 3/)/sub 2//sup +/ adds hydride and gives its stable formylacetal FpCH(OCH/sub 3/)/sub 2/, which subsequently affords the desired FpCH/sub 2/OCH/sub 3/. Thus, a unified mechanism for transforming CO or CO/sub 2/ into C/sub 1/ alkyl ligands is now available that does not traverse formyl ligands. The methylidene salt FpCH/sub 2//sup +/ (generated from FpCH/sub 2/OCH/sub 3/) picks up exogeneous CO, ascertained by a /sup 13/C labeling study, and gives the stable (eta/sup 2/-C,C) ketene complex Fp(CH/sub 2/CO)/sup +/PF/sub 6//sup -/; this complex abstracts methoxide from methanol (or even FpCH/sub 2/OMe) and provides the carbomethoxy methyl FpCH/sub 2/CO/sub 2/CH/sub 3/. This ketene complex, which effectively derives from two carbonyls, therefore serves as an efficient source of a C/sub 2/ alkyl ligand that is important in CO fixation studies. In terms of our studies on bimetallic activation of alkyl ligands we have established that the reactions of organometallic Lewis acids - e.g., CpMo(CO)/sub 3//sup +/ - with alkyl complexes entail oxidation-induced alkyl CO migratory-insertion reactions via 17-electron intermediates. Attempts at promoting hydride-CO and alkyl-CO insertion reactions with 16-electron CpMo(CO)/sub 3//sup +/ and 14-electron CpMo(CO)/sub 2//sup +/ Lewis acids are also reported. A systematic study on the preparative and subsequent reactive chemistry of bimetallic ..mu..-acetyl complexes is in progress. 23 refs.
- Research Organization:
- Rensselaer Polytechnic Inst., Troy, NY (USA)
- DOE Contract Number:
- AC02-82ER13022
- OSTI ID:
- 6735140
- Report Number(s):
- DOE/ER/13022-T1; ON: DE87006004
- Country of Publication:
- United States
- Language:
- English
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400201* -- Chemical & Physicochemical Properties
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLATION
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
HYDROGEN COMPOUNDS
HYDROGENATION
INORGANIC ACIDS
IRON COMPLEXES
KETENES
LEWIS ACIDS
LIGANDS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION INTERMEDIATES
RESEARCH PROGRAMS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES