Structural Determination and Gas-Phase Synthesis of Monomeric, Unsolvated IZnCH3 (X虄1A1): A Model Organozinc Halide

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• 作者：Matthew P. Bucchino ; Justin P. Young ; Phillip M. Sheridan ; Lucy M. Ziurys
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：November 26, 2014
• 年：2014
• 卷：118
• 期：47
• 页码：11204-11210
• 全文大小：297K
• ISSN：1520-5215

文摘

The first experimental structure of a monomeric organozinc halide, IZnCH₃, has been measured using millimeter-wave direct absorption spectroscopy in the frequency range 256鈥?93 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 (X虄¹A₁) belonging to the C_3v point group, in agreement with DFT calculations, with the following experimentally determined structural parameters: r_IZn = 2.4076(2) 脜, r_ZnC = 1.9201(2) 脜, r_CH = 1.105(9) 脜, and 鈭燞鈥揅鈥揌 = 108.7(5)掳. 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鈥搃odine bond of iodomethane.