Microwave spectrum, structural parameters, and quadrupole coupling for 1,2-dihydro-1,2-azaborine

Adam M. Daly, Chakree Tanjaroon, Adam J V Marwitz, Shih Yuan Liu, Stephen G Kukolich

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

The first microwave spectrum for 1,2-dihydro-1,2-azaborine has been measured in the frequency range 7-18 GHz, providing accurate rotational constants and nitrogen and boron quadrupole coupling strengths for three isotopomers, H6C411B14N, H 6C410B14N, and H5DC 411B14N. The measured rotational constants were used to accurately determine coordinates for the substituted atoms and provide sufficient data to determine most of the important structural parameters for this molecule. The spectra were obtained using a pulsed beam Fourier transform microwave spectrometer, with sufficient resolution to allow accurate measurements of 14N, 11B, and 10B nuclear quadrupole hyperfine interactions. High-level ab initio calculations provided structural parameters and quadrupole coupling strengths that are in very good agreement with measured values. The rotational constants for the parent compound are A = 5657.335(1), B = 5349.2807(5), and C = 2749.1281(4) MHz, yielding the inertial defect δ0 = 0.02 amua å2 for the ground-state structure. The observed near-zero and positive inertial defect clearly indicates that the molecular structure of 1,2-dihydro-1,2-azaborine is planar. The least-squares fit analysis to determine the azaborine ring structure yielded the experimental bond lengths and 2σ errors R(B-N) = 1.45(3) å, R(B-C) = 1.51(1) å, and R(N-C) = 1.37(3) å for the ground-state structure. Interbond angles for the ring were also determined. An extended Townes-Dailey population analysis of the boron and nitrogen quadrupole coupling constants provided the valence p-electron occupancy pc = 0.3e for boron and pc = 1.3e for nitrogen.

Original languageEnglish (US)
Pages (from-to)5501-5506
Number of pages6
JournalJournal of the American Chemical Society
Volume132
Issue number15
DOIs
StatePublished - Apr 21 2010

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Boron
Microwaves
Nitrogen
Ground state
Microwave spectrometers
Defects
Bond length
Fourier Analysis
Molecular Structure
Least-Squares Analysis
Molecular structure
Fourier transforms
Electrons
Atoms
Molecules
Population
1,2-azaborine

ASJC Scopus subject areas

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

Cite this

Microwave spectrum, structural parameters, and quadrupole coupling for 1,2-dihydro-1,2-azaborine. / Daly, Adam M.; Tanjaroon, Chakree; Marwitz, Adam J V; Liu, Shih Yuan; Kukolich, Stephen G.

In: Journal of the American Chemical Society, Vol. 132, No. 15, 21.04.2010, p. 5501-5506.

Research output: Contribution to journalArticle

Daly, Adam M. ; Tanjaroon, Chakree ; Marwitz, Adam J V ; Liu, Shih Yuan ; Kukolich, Stephen G. / Microwave spectrum, structural parameters, and quadrupole coupling for 1,2-dihydro-1,2-azaborine. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 15. pp. 5501-5506.
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abstract = "The first microwave spectrum for 1,2-dihydro-1,2-azaborine has been measured in the frequency range 7-18 GHz, providing accurate rotational constants and nitrogen and boron quadrupole coupling strengths for three isotopomers, H6C411B14N, H 6C410B14N, and H5DC 411B14N. The measured rotational constants were used to accurately determine coordinates for the substituted atoms and provide sufficient data to determine most of the important structural parameters for this molecule. The spectra were obtained using a pulsed beam Fourier transform microwave spectrometer, with sufficient resolution to allow accurate measurements of 14N, 11B, and 10B nuclear quadrupole hyperfine interactions. High-level ab initio calculations provided structural parameters and quadrupole coupling strengths that are in very good agreement with measured values. The rotational constants for the parent compound are A = 5657.335(1), B = 5349.2807(5), and C = 2749.1281(4) MHz, yielding the inertial defect δ0 = 0.02 amua {\aa}2 for the ground-state structure. The observed near-zero and positive inertial defect clearly indicates that the molecular structure of 1,2-dihydro-1,2-azaborine is planar. The least-squares fit analysis to determine the azaborine ring structure yielded the experimental bond lengths and 2σ errors R(B-N) = 1.45(3) {\aa}, R(B-C) = 1.51(1) {\aa}, and R(N-C) = 1.37(3) {\aa} for the ground-state structure. Interbond angles for the ring were also determined. An extended Townes-Dailey population analysis of the boron and nitrogen quadrupole coupling constants provided the valence p-electron occupancy pc = 0.3e for boron and pc = 1.3e for nitrogen.",
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AU - Liu, Shih Yuan

AU - Kukolich, Stephen G

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N2 - The first microwave spectrum for 1,2-dihydro-1,2-azaborine has been measured in the frequency range 7-18 GHz, providing accurate rotational constants and nitrogen and boron quadrupole coupling strengths for three isotopomers, H6C411B14N, H 6C410B14N, and H5DC 411B14N. The measured rotational constants were used to accurately determine coordinates for the substituted atoms and provide sufficient data to determine most of the important structural parameters for this molecule. The spectra were obtained using a pulsed beam Fourier transform microwave spectrometer, with sufficient resolution to allow accurate measurements of 14N, 11B, and 10B nuclear quadrupole hyperfine interactions. High-level ab initio calculations provided structural parameters and quadrupole coupling strengths that are in very good agreement with measured values. The rotational constants for the parent compound are A = 5657.335(1), B = 5349.2807(5), and C = 2749.1281(4) MHz, yielding the inertial defect δ0 = 0.02 amua å2 for the ground-state structure. The observed near-zero and positive inertial defect clearly indicates that the molecular structure of 1,2-dihydro-1,2-azaborine is planar. The least-squares fit analysis to determine the azaborine ring structure yielded the experimental bond lengths and 2σ errors R(B-N) = 1.45(3) å, R(B-C) = 1.51(1) å, and R(N-C) = 1.37(3) å for the ground-state structure. Interbond angles for the ring were also determined. An extended Townes-Dailey population analysis of the boron and nitrogen quadrupole coupling constants provided the valence p-electron occupancy pc = 0.3e for boron and pc = 1.3e for nitrogen.

AB - The first microwave spectrum for 1,2-dihydro-1,2-azaborine has been measured in the frequency range 7-18 GHz, providing accurate rotational constants and nitrogen and boron quadrupole coupling strengths for three isotopomers, H6C411B14N, H 6C410B14N, and H5DC 411B14N. The measured rotational constants were used to accurately determine coordinates for the substituted atoms and provide sufficient data to determine most of the important structural parameters for this molecule. The spectra were obtained using a pulsed beam Fourier transform microwave spectrometer, with sufficient resolution to allow accurate measurements of 14N, 11B, and 10B nuclear quadrupole hyperfine interactions. High-level ab initio calculations provided structural parameters and quadrupole coupling strengths that are in very good agreement with measured values. The rotational constants for the parent compound are A = 5657.335(1), B = 5349.2807(5), and C = 2749.1281(4) MHz, yielding the inertial defect δ0 = 0.02 amua å2 for the ground-state structure. The observed near-zero and positive inertial defect clearly indicates that the molecular structure of 1,2-dihydro-1,2-azaborine is planar. The least-squares fit analysis to determine the azaborine ring structure yielded the experimental bond lengths and 2σ errors R(B-N) = 1.45(3) å, R(B-C) = 1.51(1) å, and R(N-C) = 1.37(3) å for the ground-state structure. Interbond angles for the ring were also determined. An extended Townes-Dailey population analysis of the boron and nitrogen quadrupole coupling constants provided the valence p-electron occupancy pc = 0.3e for boron and pc = 1.3e for nitrogen.

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