Homogeneous carbon monoxide fixation. Progress report, May 1, 1980-December 31, 1980

Technical Report · Mon Dec 01 04:00:00 EST 1980

OSTI ID:6935038

Cutler, A R

Two carbonyl ligands on CpFe(CO)/sub 3//sup +/ (1) have been selectively converted to the C/sub 2/ organic molecules ethane, ethylene, methyl or ethyl acetate, or acetaldehyde. NaBH/sub 3/CN in methanol or ethanol thus reduces 1 to the alkoxymethyl complexes CpFe(CO)/sub 2/CH/sub 2/OR (2a, R = Me; b, R = Et). Alkoxyacetyl complexes CpFe(CO)L(COCH/sub 2/OR) (3, L = PPh/sub 3/; 4, P(OMe)/sub 3/), which are derived from 2, then serve as templates for synthesizing other C/sub 2/ coordinated ligands. Acidic isomerization of 3, 4 gives the carboalkoxymethyl compounds CpFe(CO)L(CH/sub 2/CO/sub 2/R); these eliminate alkyl acetate with excess acid. Alternatively, alkylation of 3, 4 affords stable ..cap alpha..,..beta..-dialkoxyethylidene complexes (e.g., CpFe(CO)PPh/sub 3/(C(OEt)CH/sub 2/OMe)/sup +/PF/sub 6//sup -/, (7a)) that are activated to reduction by borohydride reagents. BH/sub 4//sup -/ thus produces CpFe(CO)PPh/sub 3/(CH/sub 2/CH/sub 3/) (8), and Et/sub 3/BH/sup -/ gives CpFe(CO)PPh/sub 3/(CH/sub 2/CHO) (10). The ethyl complex 8 releases either ethylene by heating or ethane after protonation; the formylmethyl complex 10 eliminates acetaldehyde upon adding acid. Bimetallic activation of 3, 4, by forming ..mu..-acyl complexes CpFe(CO)L)CO(Mo(CO)/sub 3/Cp)CH/sub 2/OR)/sup +/, also activates alkoxyacetyl ligand to BH/sub 4//sup -/ reduction, giving the ethyl compounds CpFe(CO)L(CH/sub 2/CH/sub 3/).

• Research Organization: Wesleyan Univ., Middletown, CT (USA)
• DOE Contract Number: AC02-80ER10625
• OSTI ID: 6935038
• Report Number(s): DOE/ER/10625-1
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
BOROHYDRIDES
BORON COMPOUNDS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
CONVERSION
CYCLOALKENES
CYCLOPENTADIENE
DIENES
HYDROCARBONS
HYDROGEN COMPOUNDS
IRON COMPLEXES
MOLYBDENUM COMPLEXES
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
POLYENES
REDUCTION
RESEARCH PROGRAMS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES