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Title: Dehydrogenation, disproportionation and transfer hydrogenation reactions of formic acid catalyzed by molybdenum hydride compounds

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c4sc03128h· OSTI ID:1624914
 [1];  [1]
  1. Columbia Univ., New York, NY (United States). Dept. of Chemistry
+ Show Author Affiliations

The cyclopentadienyl molybdenum hydride compounds, CpRMo(PMe3)3-x(CO)xH (CpR = Cp, Cp*; x = 0, 1, 2 or 3), are catalysts for the dehydrogenation of formic acid, with the most active catalysts having the composition CpRMo(PMe3)2(CO)H. The mechanism of the catalytic cycle is proposed to involve (i) protonation of the molybdenum hydride complex, (ii) elimination of H2 and coordination of formate, and (iii) decarboxylation of the formate ligand to regenerate the hydride species. NMR spectroscopy indicates that the nature of the resting state depends on the composition of the catalyst. For example, (i) the resting states for the CpMo(CO)3H and CpMo(PMe3)(CO)2H systems are the hydride complexes themselves, (ii) the resting state for the CpMo(PMe3)3H system is the protonated species [CpMo(PMe3)3H2]+, and (iii) the resting state for the CpMo(PMe3)2(CO)H system is the formate complex, CpMo(PMe3)2(CO)(κ1-O2CH), in the presence of a high concentration of formic acid, but CpMo(PMe3)2(CO)H when the concentration of acid is low. While CO2 and H2 are the principal products of the catalytic reaction induced by CpRMo(PMe3)3-x(CO)xH, methanol and methyl formate are also observed. The generation of methanol is a consequence of disproportionation of formic acid, while methyl formate is a product of subsequent esterification. The disproportionation of formic acid is a manifestation of a transfer hydrogenation reaction, which may also be applied to the reduction of aldehydes and ketones. Thus, CpMo(CO)3H also catalyzes the reduction of a variety of ketones and aldehydes to alcohols by formic acid, via a mechanism that involves ionic hydrogenation.

Research Organization:
Columbia Univ., New York, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
FG02-93ER14339; DGE 11-44155
OSTI ID:
1624914
Journal Information:
Chemical Science, Vol. 6, Issue 3; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 69 works
Citation information provided by
Web of Science

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