Alcohol complexes of tungsten prepared by ionic hydrogenations of ketones

Jeong Sup Song, David J. Szalda, R Morris Bullock

Research output: Contribution to journalArticle

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Abstract

Ionic hydrogenation of acetone by Cp(CO)3WH and HOTf (OTf = OSO2CF3) gives the 2-propanol complex [Cp(CO)3W(HOiPr)]+OTf-. 1H NMR data suggest O-H⋯O hydrogen bonding between the alcohol OH and an oxygen of the triflate anion in solution, and a crystal structure of this complex shows that hydrogen bonding also exists in the solid state. The short O⋯O distance of 2.63(1) Å indicates a strong hydrogen bond. Hydrogenation of other ketones and aldehydes gives related [Cp(CO)3W(alcohol)]+OTf complexes. Aldehydes are selectively hydrogenated over ketones, and alkyl ketones are selectively hydrogenated over aromatic ketones. Hydrogenation of acetophenone gives ethylbenzene, with no intermediate tungsten complexes being observed. Reaction of 1-phenyl-1,3-butanedione with Cp(CO)3WH and HOTf gave {Cp(CO)3W[CH3CH(OH)CH2C(=O)Ph]}+ OTf-, the structure of which was determined by X-ray diffraction. The alcohol complexes [Cp(CO)3W(alcohol)]+OTf- decompose in solution to give free alcohols and Cp(CO)3WOTf. The cationic dihydride [Cp(CO)2(PMe3-W(H)2]+OTf- hydrogenates aldehydes and ketones; in these reactions a metal hydride serves as both the proton and hydride donor.

Original languageEnglish
Pages (from-to)3337-3346
Number of pages10
JournalOrganometallics
Volume20
Issue number15
DOIs
Publication statusPublished - Jul 23 2001

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Tungsten
Carbon Monoxide
Ketones
ketones
Hydrogenation
hydrogenation
tungsten
alcohols
Alcohols
aldehydes
Aldehydes
Hydrogen bonds
dihydrides
Hydrides
metal hydrides
hydrogen
acetone
hydrides
2-Propanol
hydrogen bonds

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Alcohol complexes of tungsten prepared by ionic hydrogenations of ketones. / Song, Jeong Sup; Szalda, David J.; Bullock, R Morris.

In: Organometallics, Vol. 20, No. 15, 23.07.2001, p. 3337-3346.

Research output: Contribution to journalArticle

Song, Jeong Sup ; Szalda, David J. ; Bullock, R Morris. / Alcohol complexes of tungsten prepared by ionic hydrogenations of ketones. In: Organometallics. 2001 ; Vol. 20, No. 15. pp. 3337-3346.
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N2 - Ionic hydrogenation of acetone by Cp(CO)3WH and HOTf (OTf = OSO2CF3) gives the 2-propanol complex [Cp(CO)3W(HOiPr)]+OTf-. 1H NMR data suggest O-H⋯O hydrogen bonding between the alcohol OH and an oxygen of the triflate anion in solution, and a crystal structure of this complex shows that hydrogen bonding also exists in the solid state. The short O⋯O distance of 2.63(1) Å indicates a strong hydrogen bond. Hydrogenation of other ketones and aldehydes gives related [Cp(CO)3W(alcohol)]+OTf complexes. Aldehydes are selectively hydrogenated over ketones, and alkyl ketones are selectively hydrogenated over aromatic ketones. Hydrogenation of acetophenone gives ethylbenzene, with no intermediate tungsten complexes being observed. Reaction of 1-phenyl-1,3-butanedione with Cp(CO)3WH and HOTf gave {Cp(CO)3W[CH3CH(OH)CH2C(=O)Ph]}+ OTf-, the structure of which was determined by X-ray diffraction. The alcohol complexes [Cp(CO)3W(alcohol)]+OTf- decompose in solution to give free alcohols and Cp(CO)3WOTf. The cationic dihydride [Cp(CO)2(PMe3-W(H)2]+OTf- hydrogenates aldehydes and ketones; in these reactions a metal hydride serves as both the proton and hydride donor.

AB - Ionic hydrogenation of acetone by Cp(CO)3WH and HOTf (OTf = OSO2CF3) gives the 2-propanol complex [Cp(CO)3W(HOiPr)]+OTf-. 1H NMR data suggest O-H⋯O hydrogen bonding between the alcohol OH and an oxygen of the triflate anion in solution, and a crystal structure of this complex shows that hydrogen bonding also exists in the solid state. The short O⋯O distance of 2.63(1) Å indicates a strong hydrogen bond. Hydrogenation of other ketones and aldehydes gives related [Cp(CO)3W(alcohol)]+OTf complexes. Aldehydes are selectively hydrogenated over ketones, and alkyl ketones are selectively hydrogenated over aromatic ketones. Hydrogenation of acetophenone gives ethylbenzene, with no intermediate tungsten complexes being observed. Reaction of 1-phenyl-1,3-butanedione with Cp(CO)3WH and HOTf gave {Cp(CO)3W[CH3CH(OH)CH2C(=O)Ph]}+ OTf-, the structure of which was determined by X-ray diffraction. The alcohol complexes [Cp(CO)3W(alcohol)]+OTf- decompose in solution to give free alcohols and Cp(CO)3WOTf. The cationic dihydride [Cp(CO)2(PMe3-W(H)2]+OTf- hydrogenates aldehydes and ketones; in these reactions a metal hydride serves as both the proton and hydride donor.

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