Mechanistic studies of carbon monoxide reduction. Progress report, August 1, 1979-August 1, 1980

Technical Report · Tue Jul 29 04:00:00 EDT 1980

DOI:https://doi.org/10.2172/5171368· OSTI ID:5171368

Geoffroy, G. L.

Mechanistic schemes for the metal surface catalyzed reduction of carbon monoxide to methanol and hydrocarbons have been proposed and the feasibility of these mechanisms are being tested by preparing and studying the chemistry of metal clusters which resemble the proposed surface intermediates. In an effort to prepare clusters with bound formyl groups, Os/sub 3/(CO)/sub 12/ and IR/sub 4/(CO)/sub 12/ have been treated with Li(BH(O-i-Pr)/sub 3/). Evidence for a formyl intermediate has been obtained with Os/sub 3/(CO)/sub 12/, and upon acidification of solutions containing this species, the new cluster Os/sub 3/(CO)/sub 11/CH/sub 2/ is isolated. The CH/sub 2/ group derives by the stepwise reduction of CO, and experiments directed toward delineating the mechanism of this transformation are described. Treatment of Os/sub 3/(CO)/sub 11/CH/sub 2/ with H/sub 2/ at 70 to 80/sup 0/C yields CH/sub 4/, and thus the complete stoichiometric conversion of CO to CH/sub 4/ has been achieved on an Os/sub 3/ cluster. The new clusters (PPN) (HFeRu/sub 3/(CO)/sub 13/) and (PPN)(HFe/sub 2/Ru/sub 2/(CO)/sub 13/) (PPN/sup +/ = (Ph/sub 3/P)/sub 2/N/sup +/) have been prepared in an attempt to prepare analogs of (HFe/sub 4/(CO)/sub 13/)/sup -/ which possesses an unusually bound and presumable activated CO. The crystal structures of each of these new clusters have revealed no unusual CO bonding modes and instead they adopt structures with pseudo-tetrahedral metal frameworks. Several reactions have been conducted directed toward the preparation of alkyl and acyl substituted clusters and these are described. The reaction of a series of mixed-metal clusters with CO have been studied. Each readily fragments under a CO atmosphere and for H/sub 2/FeRu/sub 3/(CO)/sub 13/ the rate and mechanism of this reaction have been determined.

• Research Organization: Pennsylvania State Univ., University Park (USA)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC02-79ER10345
• OSTI ID: 5171368
• Report Number(s): DOE/ER/10345--1
• Country of Publication: United States
• Language: English

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10 SYNTHETIC FUELS
ALCOHOLS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
HYDROCARBONS
HYDROXY COMPOUNDS
IRIDIUM COMPOUNDS
KINETICS
METHANOL
ORGANIC COMPOUNDS
OSMIUM COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
REDUCTION
RESEARCH PROGRAMS
RUTHENIUM COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS