Structural determination and gas-phase synthesis of monomeric, unsolvated IZnCH3 (X̃1a1): A model organozinc halide

Matthew P. Bucchino, Justin P. Young, Phillip M. Sheridan, Lucy M Ziurys

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Abstract

The first experimental structure of a monomeric organozinc halide, IZnCH3, has been measured using millimeter-wave direct absorption spectroscopy in the frequency range 256-293 GHz. IZnCH3 is a model compound for organozinc halides, widely used in cross-coupling reactions. The species was produced in the gas phase by reaction of zinc vapor with iodomethane in the presence of a dc discharge. IZnCH3 was identified on the basis of its pure rotational spectrum as well as those of the isotopically substituted species I66ZnCH3, I64Zn13CH3, and I64ZnCD3. IZnCH3 is unmistakably a symmetric top molecule (X̃1A1) belonging to the C3v point group, in agreement with DFT calculations, with the following experimentally determined structural parameters: rIZn = 2.4076(2) A˚, rZnC = 1.9201(2) A˚, rCH = 1.105(9) A˚, and <H-C-H = 108.7(5)°. The basic methyl group geometry is not significantly altered in this molecule. Experimental observations suggest that IZnCH3 is synthesized in the gas phase by direct insertion of activated atomic zinc into the carbon-iodine bond of iodomethane. (Figure Presented).

Original languageEnglish (US)
Pages (from-to)11204-11210
Number of pages7
JournalJournal of Physical Chemistry A
Volume118
Issue number47
DOIs
StatePublished - 2014

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halides
Zinc
zinc
Gases
vapor phases
Point groups
Molecules
cross coupling
rotational spectra
synthesis
Absorption spectroscopy
Millimeter waves
Discrete Fourier transforms
Iodine
millimeter waves
iodine
molecules
insertion
absorption spectroscopy
Carbon

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Structural determination and gas-phase synthesis of monomeric, unsolvated IZnCH3 (X̃1a1) : A model organozinc halide. / Bucchino, Matthew P.; Young, Justin P.; Sheridan, Phillip M.; Ziurys, Lucy M.

In: Journal of Physical Chemistry A, Vol. 118, No. 47, 2014, p. 11204-11210.

Research output: Contribution to journalArticle

Bucchino, Matthew P. ; Young, Justin P. ; Sheridan, Phillip M. ; Ziurys, Lucy M. / Structural determination and gas-phase synthesis of monomeric, unsolvated IZnCH3 (X̃1a1) : A model organozinc halide. In: Journal of Physical Chemistry A. 2014 ; Vol. 118, No. 47. pp. 11204-11210.
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abstract = "The first experimental structure of a monomeric organozinc halide, IZnCH3, has been measured using millimeter-wave direct absorption spectroscopy in the frequency range 256-293 GHz. IZnCH3 is a model compound for organozinc halides, widely used in cross-coupling reactions. The species was produced in the gas phase by reaction of zinc vapor with iodomethane in the presence of a dc discharge. IZnCH3 was identified on the basis of its pure rotational spectrum as well as those of the isotopically substituted species I66ZnCH3, I64Zn13CH3, and I64ZnCD3. IZnCH3 is unmistakably a symmetric top molecule (X̃1A1) belonging to the C3v point group, in agreement with DFT calculations, with the following experimentally determined structural parameters: rIZn = 2.4076(2) A˚, rZnC = 1.9201(2) A˚, rCH = 1.105(9) A˚, and <H-C-H = 108.7(5)°. The basic methyl group geometry is not significantly altered in this molecule. Experimental observations suggest that IZnCH3 is synthesized in the gas phase by direct insertion of activated atomic zinc into the carbon-iodine bond of iodomethane. (Figure Presented).",
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AB - The first experimental structure of a monomeric organozinc halide, IZnCH3, has been measured using millimeter-wave direct absorption spectroscopy in the frequency range 256-293 GHz. IZnCH3 is a model compound for organozinc halides, widely used in cross-coupling reactions. The species was produced in the gas phase by reaction of zinc vapor with iodomethane in the presence of a dc discharge. IZnCH3 was identified on the basis of its pure rotational spectrum as well as those of the isotopically substituted species I66ZnCH3, I64Zn13CH3, and I64ZnCD3. IZnCH3 is unmistakably a symmetric top molecule (X̃1A1) belonging to the C3v point group, in agreement with DFT calculations, with the following experimentally determined structural parameters: rIZn = 2.4076(2) A˚, rZnC = 1.9201(2) A˚, rCH = 1.105(9) A˚, and <H-C-H = 108.7(5)°. The basic methyl group geometry is not significantly altered in this molecule. Experimental observations suggest that IZnCH3 is synthesized in the gas phase by direct insertion of activated atomic zinc into the carbon-iodine bond of iodomethane. (Figure Presented).

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