Hydride transfer reactions of transition metal hydrides in the preparation of [Cp(CO)3W(η1-aldehyde)]+OTf- and [Cp(CO)3W(η1-ketone)]+OTf- complexes

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

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

The reaction of Ph(C=O)Cl with Cp(CO)3WH and HOTf gives the η1-aldehyde complex [Cp(CO)3W(η1-PhCHO)]+OTf-. The structure of [Cp(CO)3W(η1-PhCHO)]+OTf- (C16H11F3O7SW) was determined by single crystal X-ray diffraction (triclinic, space group P1̄, a = 10.639(5), b = 10.752(4), c = 10.096(3) Å, α = 91.38(3), β = 117.08(3), γ = 66.01(4)°, Z = 2). Decomposition of this compound in CH2Cl2 solution follows first-order kinetics (k = 3.6(2) × 10-4 s-1 at 25°C) and produces free PhCHO and Cp(CO)3WOTf. The η1-CH3CHO complex [Cp(CO)3W(η1-CH3CHO)]+ OTf- was similarly prepared from the reaction of acetyl chloride with Cp(CO)3WH and HOTf. Hydrogenation of αβ-unsaturated aldehydes by Cp(CO)3WH and HOTf produces [Cp(CO)3W(η1-RCHO)]+OTf- complexes that were isolated and fully characterized; analogous reactions with α,β-unsaturated ketones gives [Cp(CO)3W(η1-O = CRR′)]+OTf- complexes. All of these aldehyde and ketone complexes with OTf- release free aldehyde or ketone in solution and produce Cp(CO)3WOTf, but [Cp(CO)3W(η1-2-butanone)]+BAr′ 4- (Ar′ = 3,5-bis(trifluoromethyl)phenyl) is much more stable.

Original languageEnglish
Pages (from-to)161-172
Number of pages12
JournalInorganica Chimica Acta
Volume259
Issue number1-2
DOIs
Publication statusPublished - Jun 1997

Keywords

  • Aldehyde complexes
  • Crystal structures
  • Hydride complexes
  • Hydrogenation
  • Ketone complexes
  • Tungsten complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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