NHC-induced conversion of a W–Ge double bond into the triple bond through formation of W–Ge single and double bonded intermediates

Tetsuya Fukuda, Hisako Hashimoto, Hiromi Tobita

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

Reaction of hydrido(hydrogermylene) complex Cp*(CO)2(H)W=Ge(H)(Tsi) (1, Tsi = C(SiMe3)3) with 1 equiv of MeIMe (MeIMe = 1,3-dimethyl-4,5-dimethylimidazol-2-ylidene) immediately afforded NHC-stabilized germylene complex Cp*(CO)2(H)WGe(H)(MeIMe)(Tsi) (2) that has a zwitterionic, W–Ge single-bonded structure. Complex 2 was thermally unstable and intramolecular proton-transfer followed by hydride-transfer to the NHC-unit occurred slowly at room temperature to give anionic germylene complex [Cp*(CO)2W=Ge(H)(Tsi)][HMeIMe] ([3][HMeIMe]) first and subsequently germylyne complex Cp*(CO)2W≡Ge(Tsi) (4) and H2MeIMe. Although [3][HMeIMe] was too unstable to be isolated, the salt of bulkier [HMeIiPr]+, [Cp*(CO)2W=Ge(H)(Tsi)][HMeIiPr] ([3][HMeIiPr]), was thermally more stable and was isolated and fully characterized.

Original languageEnglish
Pages (from-to)89-94
Number of pages6
JournalJournal of Organometallic Chemistry
Volume848
DOIs
Publication statusPublished - 2017 Jan 1

Keywords

  • Germylene complex
  • Germylyne complex
  • Hydride transfer
  • NHC-carbene
  • Proton transfer
  • X-ray diffraction

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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