Borane Carbonyl Research Articles

High resolution infrared spectra and structure of borine carbonyl: The analysis of the ν2 bands of 11BD 3CO and 10BD 3CO

The high resolution infrared spectra of 10BD 3CO and 11BD 3CO were obtained in the region of the ν 2 fundamentals. The K = 0 subbands of the ν 2 and ν 2 + ν 8 − ν 8 bands were assigned. The K structure is unresolvable with a spectral slit width of 0.03 cm −1. A series, almost as strong as the main series, has been identified in the spectrum of the 11B molecule but has not been assigned. It is shown that the four structural parameters of borine carbonyl cannot be accurately determined using only the B 0 rotational constants of four isotopically substituted molecules.

Molecular orbital calculation of the electronic structure of borane carbonyl

Molecular orbital calculation of the electronic structure of borane carbonyl

High resolution infrared absorption spectrum of borine carbonyl: The analysis of ν4 and ν4 + ν8 − ν8 of 11BH 3CO

The BC stretching vibration, designated as ν 4 (in the region of 14.5 μm) gives rise to a parallel band. This band has been measured with sufficient resolution (0.026–0.034 cm −1) to resolve the subbands corresponding to values of K ≧ 5. The band origin and the rotational constants were obtained from a complete rotational analysis. The ground state rotational constants B and D JK agree, within experimental error, with those derived from the microwave spectrum. Values of the band origin and the rotational constants, B and D JK , for the first excited vibrational states of ν 8 and ν 4 + ν 8 have been determined from the rotational analysis of the K = 0 subband of the main “hot” band ν 4 + ν 8 − ν 8.

Molecular constants of borine carbonyl

All the molecular vibrational constants for 11BH 3CO, 10BH 3CO, 11BD 3CO and 10BD 3CO have been calculated using the tentatively standardized set of symmetry coordinates. It is found that the results are not in good agreement with the results of previous workers.

Infrared spectra of the pyrolysis products of borane carbonyl in an argon matrix

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTInfrared spectra of the pyrolysis products of borane carbonyl in an argon matrixAndrew Kaldor and Richard Francis PorterCite this: J. Am. Chem. Soc. 1971, 93, 9, 2140–2145Publication Date (Print):May 1, 1971Publication History Published online1 May 2002Published inissue 1 May 1971https://doi.org/10.1021/ja00738a008RIGHTS & PERMISSIONSArticle Views173Altmetric-Citations44LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (609 KB) Get e-Alerts Get e-Alerts

Preparation of borane in high absolute yield from borane carbonyl

Preparation of borane in high absolute yield from borane carbonyl

Mass spectrometric investigation of the fragmentation pattern and the pyrolysis of borane carbonyl

Mass spectrometric investigation of the fragmentation pattern and the pyrolysis of borane carbonyl

Molecular Energetics of Borane Carbonyl and the Symmetric Dissociation Energy of Diborane

Large concentrations of borane, BH3, are produced upon the pyrolysis of borane carbonyl. Ionization efficiency measurements using a fast inlet mass-spectrometric technique, have led to I(BH3) as well as A(B+), A(BH+), A(BH2+), and A(BH3+) from BH3CO. These numbers permit a complete development of the molecular energetics of BH3CO and a confirmation of the symmetric dissociation energy of diborane of 59 kcal/mole. Earlier equilibrium data on the BH3CO decomposition, combined with these electron-impact data, also confirm D(BH3–BH3) = 59 kcal/mole. Earlier kinetic studies that suggest a very much lower dissociation energy are shown to be equivocal at best.

Mass spectrometric investigation of the low-pressure pyrolysis of borane carbonyl. Bond dissociation energy of diborane

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMass spectrometric investigation of the low-pressure pyrolysis of borane carbonyl. Bond dissociation energy of diboraneThomas P. Fehlner and G. W. MappesCite this: J. Phys. Chem. 1969, 73, 4, 873–882Publication Date (Print):April 1, 1969Publication History Published online1 May 2002Published inissue 1 April 1969https://doi.org/10.1021/j100724a020RIGHTS & PERMISSIONSArticle Views129Altmetric-Citations30LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts

The hydrogenation of boron monoxide to diborane and the reactions of boron and boron carbide with titanium and zirconium dioxides

Hydrogenation of boron monoxide or of systems producing it in situ, e.g. a mixture of boric oxide and carbon, above 1000° and at atmospheric pressure, yields diborane (or borine carbonyl) probably via the intermediate formation of boroxine. The reactions of boron and boron carbide with titanium and zirconium dioxides above 1100° in vacuo lead to the formation of the metal diborides and the volatile boron monoxide.

Reactions of co-ordinated boron compounds in the gas phase. Part I. Borine carbonyl and trimethylamine

Download options Please wait... Article information DOI https://doi.org/10.1039/J19660001034 Article type Paper Download Citation J. Chem. Soc. A, 1966, 1034-1037 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Reactions of co-ordinated boron compounds in the gas phase. Part I. Borine carbonyl and trimethylamine J. Grotewold, E. A. Lissi and A. E. Villa, J. Chem. Soc. A, 1966, 1034 DOI: 10.1039/J19660001034 To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author J. Grotewold E. A. Lissi A. E. Villa

Boroxine. A New Route to Borane Carbonyl

Boroxine. A New Route to Borane Carbonyl

Reactions of co-ordinated boron compounds in the gas phase. Part II. Triethylamine as scavanger of borine

The thermal decomposition of borine carbonyl has been carried out in the presence of triethylamine, a very suitable scavenger of borine (BH3). The bimolecular reaction does not compete with the unimolecular rupture of the B–C bond. At 0°, the pressure-dependence of the unimolecular rupture has been studied, kunimol being equal to ½k∞ at 90 torr when propane is used as third body. From the value of k∞, and assuming a value of 1013·4 sec.–1 for the pre-exponential factor A, the activation energy is Ea= 21·4 ± 1·2 kcal./mole. The dissociation energy of the B–B bond in diborane is then calculated to be D(B–B)= 33·5 ± 2·4 kcal./mole, if the recombination reaction of borine and carbon monoxide has Ea= 0.

The absorption spectrum of BH and BD in the vacuum ultraviolet

The absorption spectrum of the BH radical has been obtained in the flash photolysis of borine carbonyl. Eleven new electronic transitions have been found which establish eight new electronic states and extend the available information on two others. Most of the upper electronic states are Rydberg states and, although no extended Rydberg series have been found, a value of the ionization potential of 9.77 ± 0.05 eV has been derived from them. Several of the excited states show the effects of strong l-uncoupling which is expected for Rydberg states but has been observed hitherto only for H 2 and He 2. The uncoupling effects in the 3 p complex of BH are well represented by the formulas of Dieke and Weizel but for the 3 d complex the corresponding formulas of Kovács and Budó had to be modified since the zero rotation energies of Σ, Π, and Δ states are not proportional to Λ 2 as required by these formulas. Values for the rotational and vibrational constants of most of the new electronic states have been derived and those for the known states have been improved. Corresponding data for BD have also been obtained. The observed isotope shifts between BH and BD in the B- X system can be made to fit the standard formulas only if an electronic isotope shift of 15 ·4 cm −1 is assumed.

Comments on the Vibrational Spectrum of Borine Carbonyl

First Page

Nuclear Quadrupole Interaction in Boron Compounds

The quadrupole coupling constants of B11 in some boron compounds are investigated in detail. A Townes-and-Dailey type of interpretation for boron trimethyl gives better agreement with experiment than a detailed molecular orbital calculation, but it is pointed out that this agreement is to be regarded as fortuitous. It is concluded that if localized LCAOMO functions are formed from undistorted atomic orbitals to describe a bond, they lead to an underestimation of the field gradient at the nucleus due to the electrons. For borine carbonyl, an estimation of the ionic character of the BC bond is made from the observed quadrupole coupling constant of B11. With this estimate, the dipole moment associated with the BH3 group is obtained from the observed dipole moment of the whole molecule. The dipole moment of the BH3 group is also calculated using localized LCAOMO's for the BH bonds. This calculation gives the correct sign of the observed dipole moment, but overestimates its magnitude. Some comments are made on the quadrupole interaction tensor for B11 in kernite using a molecular orbital approach.

Vibrational Spectrum of Borine Carbonyl

The infrared spectra of both solid and gaseous BH3CO, 10BH3CO, BD3CO, and 10BD3CO have been obtained. In addition some observations have been made on the Raman spectra of the gaseous compounds. Fundamental frequencies have been assigned to all normal modes and the vibrational potential constants for borine carbonyl have been approximated by means of a simplified force field.

Thermodynamic Functions for Borine Carbonyl

Thermodynamic Functions for Borine Carbonyl

The Mechanism of Decomposition of Borine Carbonyl

The Mechanism of Decomposition of Borine Carbonyl

The Infra-Red Spectrum of Borine Carbonyl and a Normal Coordinate Analysis of Axial WXYZ3 Molecules

The infra-red spectrum of borine carbonyl has been investigated in the region 2 to 25μ. Two perpendicular-type bands have been partially resolved, and indicate that the molecule is a symmetric top with symmetry C3v. A normal coordinate analysis of axial WXYZ3 molecules has been carried out and applied to H3BCO, the following values having been obtained for the force constants: kCO=17.3, kBC=2.97, kBH=3.21, kBCO=0.142, kHBC=0.333, kHBH=0.363, all in units of 105 dynes/cm.