Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Trinuclear osmium clusters as models for intermediates in carbon monoxide reduction chemistry. 1. Stepwise reduction of CO to a. mu. -CH/sub 2/ ligand on an Os/sub 3/ cluster face

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00321a601· OSTI ID:6805196
Treatment of Os/sub 3/(CO)/sub 12/ in tetrahydrofuran (THF) with K(BH(O-i-Pr)/sub 3/) at 0/sup 0/C gives an unstable formyl complex K(Os/sub 3/(CO)/sub 11/(CHO)) (1). Acidification of THF solutions of 1 with aqueous 20% H/sub 3/PO/sub 4/ yields the new cluster Os/sub 3/(CO)/sub 11/(..mu..-CH/sub 2/) which has been spectroscopically characterized. Attempted alkylation of 1 with ((CH/sub 3/)/sub 3/O)BF/sub 4/ also gave Os/sub 3/(CO)/sub 11/(..mu..-CH/sub 2/). Methane is produced when Os/sub 3/(CO)/sub 11/(..mu..-CH/sub 2/) is heated under an H/sub 2/ atmosphere, but when the mixture is heated in the absence of H/sub 2/, CO loss occurs to yield H/sub 2/Os/sub 3/(CO)/sub 9/(..mu../sub 3/-CCO), which has been spectroscopically characterized. The mechanism of the (Os/sub 3/(CO)/sub 11/(CHO))/sup -/ to Os/sub 3/(CO)/sub 11/(..mu..-CH/sub 2/) transformation is discussed as well as the possible relevance of these results to CO reduction on metal surfaces.
Research Organization:
Pennsylvania State Univ., University Park
OSTI ID:
6805196
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 106:9; ISSN JACSA
Country of Publication:
United States
Language:
English