Microwave spectra for (C6H5D)Cr(CO)3, (C6D6)Cr(CO)3, and (C6H5F)Cr(CO)3 and the structure of (benzene)chromium tricarbonyl

S. M. Sickafoose, S. M. Breckenridge, Stephen G Kukolich

Research output: Contribution to journalArticle

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Abstract

Microwave spectra for the D1 and D6 isotopomers of (benzene)chromium tricarbonyl and (fluorobenzene)chromium tricarbonyl were measured using a Flygare-Balle type microwave spectrometer system. The new rotational constants for the deuterium-substituted isotopomers are used with previous data which include 13C isotopomers to obtain a gas-phase structure for (benzene)chromium tricarbonyl. The new rotational constant for the C6D6, symmetric-top, isotopomer is B(bz-d6) = 698.6934(1) MHz. Asymmetric-top structure were observed for a single deuterium substitution on benzene, giving B(bz-d1) = 730.0491(4) MHz and C(bz-d1) = 723.6641(4) MHz. Rotational constants obtained for (fluorobenzene)chromium tricarbonyl are A = 814.1491(2) MHz, B = 641.1594(2) MHz, and C = 586.5866(1) MHx. The centrifugal distortion constants are small, with DJ ≅ 0.05 kHz. Structural parameters determined are center of the benzene carbon plane to chromium distance r(Cr-bz) = 1.66(2) Å, the chromium to carbonyl carbon bond length r(Cr-CO ) = 1.876(7) Å, the benzene carbon to hydrogen bond length r(C-H) = 1.080(3) Å, and the carbonyl carbon to oxygen bond length r(C-O) = 1.148(7) Å. The OC-Cr-CO interbond angle is α = 87.4(6)°. The average benzene C-C bond length is 1.413(4) Å. A small isotopic shift in the 53Cr quadrupole coupling strength was observed for the C6D6 isotopomer relative to the normal isotopomer. The hydrogen atoms are displaced out of the benzene carbon plane toward the Cr atom with the C-H bond axis at an angle γ = 2.8(2)° with respect to the benzene carbon plane.

Original languageEnglish (US)
Pages (from-to)5176-5179
Number of pages4
JournalInorganic Chemistry
Volume33
Issue number23
StatePublished - 1994

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Fluorobenzenes
microwave spectra
Chromium
Carbon Monoxide
Benzene
chromium
benzene
Microwaves
Carbon
Bond length
carbon
Deuterium
deuterium
Microwave spectrometers
microwave spectrometers
Atoms
Phase structure
Hydrogen
hydrogen atoms
Hydrogen bonds

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Microwave spectra for (C6H5D)Cr(CO)3, (C6D6)Cr(CO)3, and (C6H5F)Cr(CO)3 and the structure of (benzene)chromium tricarbonyl. / Sickafoose, S. M.; Breckenridge, S. M.; Kukolich, Stephen G.

In: Inorganic Chemistry, Vol. 33, No. 23, 1994, p. 5176-5179.

Research output: Contribution to journalArticle

@article{93c095b52e344a668c2ba757883e0768,
title = "Microwave spectra for (C6H5D)Cr(CO)3, (C6D6)Cr(CO)3, and (C6H5F)Cr(CO)3 and the structure of (benzene)chromium tricarbonyl",
abstract = "Microwave spectra for the D1 and D6 isotopomers of (benzene)chromium tricarbonyl and (fluorobenzene)chromium tricarbonyl were measured using a Flygare-Balle type microwave spectrometer system. The new rotational constants for the deuterium-substituted isotopomers are used with previous data which include 13C isotopomers to obtain a gas-phase structure for (benzene)chromium tricarbonyl. The new rotational constant for the C6D6, symmetric-top, isotopomer is B(bz-d6) = 698.6934(1) MHz. Asymmetric-top structure were observed for a single deuterium substitution on benzene, giving B(bz-d1) = 730.0491(4) MHz and C(bz-d1) = 723.6641(4) MHz. Rotational constants obtained for (fluorobenzene)chromium tricarbonyl are A = 814.1491(2) MHz, B = 641.1594(2) MHz, and C = 586.5866(1) MHx. The centrifugal distortion constants are small, with DJ ≅ 0.05 kHz. Structural parameters determined are center of the benzene carbon plane to chromium distance r(Cr-bz) = 1.66(2) {\AA}, the chromium to carbonyl carbon bond length r(Cr-CO ) = 1.876(7) {\AA}, the benzene carbon to hydrogen bond length r(C-H) = 1.080(3) {\AA}, and the carbonyl carbon to oxygen bond length r(C-O) = 1.148(7) {\AA}. The OC-Cr-CO interbond angle is α = 87.4(6)°. The average benzene C-C bond length is 1.413(4) {\AA}. A small isotopic shift in the 53Cr quadrupole coupling strength was observed for the C6D6 isotopomer relative to the normal isotopomer. The hydrogen atoms are displaced out of the benzene carbon plane toward the Cr atom with the C-H bond axis at an angle γ = 2.8(2)° with respect to the benzene carbon plane.",
author = "Sickafoose, {S. M.} and Breckenridge, {S. M.} and Kukolich, {Stephen G}",
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T1 - Microwave spectra for (C6H5D)Cr(CO)3, (C6D6)Cr(CO)3, and (C6H5F)Cr(CO)3 and the structure of (benzene)chromium tricarbonyl

AU - Sickafoose, S. M.

AU - Breckenridge, S. M.

AU - Kukolich, Stephen G

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N2 - Microwave spectra for the D1 and D6 isotopomers of (benzene)chromium tricarbonyl and (fluorobenzene)chromium tricarbonyl were measured using a Flygare-Balle type microwave spectrometer system. The new rotational constants for the deuterium-substituted isotopomers are used with previous data which include 13C isotopomers to obtain a gas-phase structure for (benzene)chromium tricarbonyl. The new rotational constant for the C6D6, symmetric-top, isotopomer is B(bz-d6) = 698.6934(1) MHz. Asymmetric-top structure were observed for a single deuterium substitution on benzene, giving B(bz-d1) = 730.0491(4) MHz and C(bz-d1) = 723.6641(4) MHz. Rotational constants obtained for (fluorobenzene)chromium tricarbonyl are A = 814.1491(2) MHz, B = 641.1594(2) MHz, and C = 586.5866(1) MHx. The centrifugal distortion constants are small, with DJ ≅ 0.05 kHz. Structural parameters determined are center of the benzene carbon plane to chromium distance r(Cr-bz) = 1.66(2) Å, the chromium to carbonyl carbon bond length r(Cr-CO ) = 1.876(7) Å, the benzene carbon to hydrogen bond length r(C-H) = 1.080(3) Å, and the carbonyl carbon to oxygen bond length r(C-O) = 1.148(7) Å. The OC-Cr-CO interbond angle is α = 87.4(6)°. The average benzene C-C bond length is 1.413(4) Å. A small isotopic shift in the 53Cr quadrupole coupling strength was observed for the C6D6 isotopomer relative to the normal isotopomer. The hydrogen atoms are displaced out of the benzene carbon plane toward the Cr atom with the C-H bond axis at an angle γ = 2.8(2)° with respect to the benzene carbon plane.

AB - Microwave spectra for the D1 and D6 isotopomers of (benzene)chromium tricarbonyl and (fluorobenzene)chromium tricarbonyl were measured using a Flygare-Balle type microwave spectrometer system. The new rotational constants for the deuterium-substituted isotopomers are used with previous data which include 13C isotopomers to obtain a gas-phase structure for (benzene)chromium tricarbonyl. The new rotational constant for the C6D6, symmetric-top, isotopomer is B(bz-d6) = 698.6934(1) MHz. Asymmetric-top structure were observed for a single deuterium substitution on benzene, giving B(bz-d1) = 730.0491(4) MHz and C(bz-d1) = 723.6641(4) MHz. Rotational constants obtained for (fluorobenzene)chromium tricarbonyl are A = 814.1491(2) MHz, B = 641.1594(2) MHz, and C = 586.5866(1) MHx. The centrifugal distortion constants are small, with DJ ≅ 0.05 kHz. Structural parameters determined are center of the benzene carbon plane to chromium distance r(Cr-bz) = 1.66(2) Å, the chromium to carbonyl carbon bond length r(Cr-CO ) = 1.876(7) Å, the benzene carbon to hydrogen bond length r(C-H) = 1.080(3) Å, and the carbonyl carbon to oxygen bond length r(C-O) = 1.148(7) Å. The OC-Cr-CO interbond angle is α = 87.4(6)°. The average benzene C-C bond length is 1.413(4) Å. A small isotopic shift in the 53Cr quadrupole coupling strength was observed for the C6D6 isotopomer relative to the normal isotopomer. The hydrogen atoms are displaced out of the benzene carbon plane toward the Cr atom with the C-H bond axis at an angle γ = 2.8(2)° with respect to the benzene carbon plane.

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