The End of a 30-Year-Old Controversy? A Computational Study of the B−N Stretching Frequency of BH<sub>3</sub>−NH<sub>3</sub>in the Solid State

Dillen, Jan; Verhoeven, Paul F.M.

doi:10.1021/jp027240g

Cited by 57 publications

(102 citation statements)

References 37 publications

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“…20 In agreement with the structural change, the BN stretching frequency increases by 200 cm -1 when going from the gas phase to the solid state. 21 Note that an even more pronounced (0.4 Å) contraction of the BN bond occurs for CH 3 CN · BF 3 . 22 Elongated bonds are often difficult to describe ab initio with high precision.…”

Section: Introductionmentioning

confidence: 97%

Equilibrium Structure and Torsional Barrier of BH₃NH₃

et al. 2008

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Born-Oppenheimer equilibrium structures, r(e)(BO), of the electronic ground state of the borazane (BH3NH3) molecule of C3v point-group symmetry are computed ab initio using the CCSD(T) method with basis sets up to quintuple-zeta quality. Inclusion of the counterpoise correction and extrapolation of the structural parameters to the complete basis set limit yield a best estimate of r(e)(BO) of BH3NH3. The anharmonic force field of BH3NH3, computed at the CCSD(T) level of theory with a basis set of triple-zeta quality, allows the determination of semi-experimental equilibrium rotational constants, which in turn result in a semi-experimental equilibrium structure, r(e)(SE). The r(e)(BO) and r(e)(SE) structures are in excellent agreement, indicating the validity of the methods used for their determination. The empirical mass-dependent structure, r(m)(1), of BH3NH3 is also determined. Although it is inferior in quality to the previous two structures, it is much more accurate than the standard empirical r0 and r(s) structures reported earlier for BH3NH3. The semi-experimental r(e)(SE) as well as the empirical r(m)(1) structures determined are based on experimental ground-state rotational constants available from the literature for nine isotopologues of borazane. The effective barrier to the internal rotation of BH3NH3, a molecule isoelectronic with CH3CH3, has been computed ab initio, employing the focal-point analysis (FPA) approach, to be 699 +/- 11 cm(-1). This compares favorably with an empirical redetermination of the effective barrier based on the above r(e)(SE) structure, V3 = 718(17) cm(-1).

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Section: Introductionmentioning

confidence: 97%

Equilibrium Structure and Torsional Barrier of BH₃NH₃

et al. 2008

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“…12 NH 3 BH 3 has been the subject of many theoretical calculations that have examined the role of DHB in the electron density distribution, charge transfer, molecular conformations, and reaction mechanisms. [13][14][15][16][17][18][13][14][15][16][17] show that the strongly polar N-H and weakly polar B-H bond is responsible for the bent configuration of NH 3 BH 3 dimer, resulting in an almost linear N-H¯H bond angle ͑150°-160°͒ and H¯H-B angle of ͑105°-110°͒, in agreement with the structural data ͑156°and 106°, respectively͒. [4][5][6] The mutual degree of penetration of H atom from the N-H bond into the H atom from the B-H bond has been taken as an indication of the strength of the dihydrogen bond and varies within the structure.…”

Section: Pressure-induced Complexation Of Nh 3 Bh 3 -H 2 I Introductionmentioning

confidence: 99%

Pressure-induced complexation of NH3BH3–H2

Chellappa¹,

Somayazulu²,

Struzhkin³

et al. 2009

The Journal of Chemical Physics

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High pressure Raman spectroscopy of NH 3 BH 3 -H 2 mixtures up to 60 GPa reveals unusual pressure-induced complexation and intermolecular interactions. Stretching modes of H 2 in the complex arise at 6.7 and 10 GPa, increasing in frequency with pressure of up to 60 GPa with different pressure coefficients, and at ϳ40 GPa, the lower frequency mode approaches vibron frequency of bulk H 2 . Pressure-induced transformations in pure NH 3 BH 3 studied up to 60 GPa reveal a disorder-order transition at 1 GPa ͑phase II͒ and further transitions at 5 ͑phase III͒ and 10 GPa ͑phase IV͒. The spectra of both pure NH 3 BH 3 and the NH 3 BH 3 -H 2 complex provide evidence for strengthened of the N -H ␦+¯H␦− -B dihydrogen bonding linkages up to 50 GPa, beyond which they weaken. The dihydrogen bonding breaks down due to interactions with H 2 between 15 and 20 GPa in the NH 3 BH 3 -H 2 complex. The behavior of the ͑NH 3 ͒ modes in the NH 3 BH 3 -H 2 complex indicates a dominant role of the NH 3 functional group in the observed interactions.

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“…Attempts to assign the same motion in the smaller dative‐bonded prototype BH 3 NH 3 are, unfortunately, more challenging, because the BN dative bond is acutely sensitive to its environment. Intermolecular dihydrogen bonds, such as those found in the room‐temperature crystal structure, can increase the BN stretching frequency by as much as 200 wavenumbers relative to an isolated BH 3 NH 3 molecule in the gas phase 42. In the case of the MIDA esters, however, dihydrogen bonding interactions cannot occur, because the BN dative bond is fully encapsulated.…”

Section: Introductionmentioning

confidence: 99%

Characterizing the BP Stretching Vibration in Phosphorus‐Substituted Phosphine Boranes

2014

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The experimental Raman spectra of three phosphorus-substituted phosphine boranes with bulky hydrocarbon substituents are presented and compared to the results of electronic structure computations by using the M06-2X method and the 6-311G(2df, 2pd) basis set. Total-energy distributions (TEDs) are calculated to describe the degree of mixing of the dative-bond stretching vibration with other simple internal coordinates. This level of theory is found to accurately reproduce the B-P stretching frequency in all three crystalline solids. The Raman spectra of five smaller B-P-containing molecules, including BH(3) PH(3), are also simulated at this level of theory and compared to previous experimental results.

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The End of a 30-Year-Old Controversy? A Computational Study of the B−N Stretching Frequency of BH₃−NH₃in the Solid State

Cited by 57 publications

References 37 publications

Equilibrium Structure and Torsional Barrier of BH₃NH₃

Equilibrium Structure and Torsional Barrier of BH₃NH₃

Pressure-induced complexation of NH3BH3–H2

Characterizing the BP Stretching Vibration in Phosphorus‐Substituted Phosphine Boranes

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The End of a 30-Year-Old Controversy? A Computational Study of the B−N Stretching Frequency of BH3−NH3in the Solid State

Cited by 57 publications

References 37 publications

Equilibrium Structure and Torsional Barrier of BH3NH3

Equilibrium Structure and Torsional Barrier of BH3NH3

Pressure-induced complexation of NH3BH3–H2

Characterizing the BP Stretching Vibration in Phosphorus‐Substituted Phosphine Boranes

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The End of a 30-Year-Old Controversy? A Computational Study of the B−N Stretching Frequency of BH₃−NH₃in the Solid State

Equilibrium Structure and Torsional Barrier of BH₃NH₃

Equilibrium Structure and Torsional Barrier of BH₃NH₃