Journal
ADVANCED SYNTHESIS & CATALYSIS
Volume 351, Issue 5, Pages 789-800Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/adsc.200800685
Keywords
deoxygenation; dihydrogen complexes; heterolytic reaction; homogeneous catalysis; metal hydrides; ruthenium
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Funding
- US Department of Energy [DE-AC02-98CH10886]
- Office of Basic Energy Sciences, Division of Chemical Sciences
- NSERC (Canada)
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Deoxygenation of 1,2-propanediol (1.0M in sulfolane) catalyzed by bis(dicarbonyl)(mu-hydrido) (pentamethylcyclopentadiene)ruthenium trifluoromethanesulfonate ({[Cp*Ru(CO)(2)](2)(mu-H)}+OTf-) (0.5 mol%) at 110 degrees C under hydrogen (750 psi) in the presence of trifluoromethanesulfonic acid (HOTf) (60 mM) gives n-propanol as the major product, indicating high selectivity for deoxygenation of the internal hydroxy group over the terminal hydroxy group of the diol. The deoxygenation of 1,2-propanediol is strongly influenced by the concentration of acid, giving faster rates and proceeding to higher conversions as the concentration of HOTf is increased. Propionaldehyde was observed as an intermediate, being formed through acid-catalyzed dehydration of 1,2-propanediol. This aldehyde is hydrogenated to n-propanol through an Ionic pathway involving protonation of the aldehyde, followed by hydride transfer from the neutral hydride, dicarbonyl(pentamethylcyclopentadiene)ruthenium hydride [Cp*Ru(CO)(2)H]. The proposed mechanism for the deoxygenation/hydrogenation reaction involves formation of a highly acidic dihydrogen complex [Cp*Ru(CO)(2)(eta(2)-H-2)]+OTf-.
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