Activation of methane by zinc: Gas-phase synthesis, structure, and bonding of HZnCH3

Michael A. Flory, Aldo J. Apponi, Lindsay N. Zack, Lucy M. Ziurys

Research output: Contribution to journalArticle

27 Scopus citations

Abstract

The methylzinc hydride molecule, HZnCH3, has been observed in the gas phase for the first time in the monomeric form using high-resolution spectroscopic techniques. The molecule was synthesized by two methods: the reaction of dimethylzinc with hydrogen gas and methane in an AC discharge and the reaction of zinc vapor produced in a Broida-type oven with methane in a DC discharge. HZnCH3 was identified on the basis of its pure rotational spectrum, which was recorded using millimeter/submillimeter direct-absorption and Fourier transform microwave techniques over the frequency ranges 332-516 GHz and 18-41 GHz, respectively. Multiple rotational transitions were measured for this molecule in seven isotopic variants. K-ladder structure was clearly present in all of the spectra, indicating a molecule with C3v symmetry and a 1A1 ground electronic state. Extensive quadrupole hyperfine structure arising from the 67Zn nucleus was observed for the H67ZnCH3 species, suggesting covalent bonding to the zinc atom. From the multiple isotopic substitutions, a precise structure for HZnCH3 has been determined. The influence of the axial hydrogen atom slightly distorts the methyl group but stabilizes the Zn-C bond. This study suggests that HZnCH3 can be formed through the oxidative addition of zinc to methane in the gas phase under certain conditions. HZnCH3 is the first metal-methane insertion complex to be structurally characterized.

Original languageEnglish (US)
Pages (from-to)17186-17192
Number of pages7
JournalJournal of the American Chemical Society
Volume132
Issue number48
DOIs
StatePublished - Dec 8 2010

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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