Evidence of Dihydrogen Bonding of a Chiral Amine–Borane Complex in Solution by VCD Spectroscopy

Merten, Christian; Berger, Chris; McDonald, Robert; Xu, Yunjie

doi:10.1002/anie.201403690

Cited by 31 publications

(47 citation statements)

References 43 publications

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“…The B-H stretching vibration is assigned in the VCD bands of MAB at 2468.7 cm −1 . It is in good agreement with the experimental results observed by Merten [17]. The intensity of this band is strengthened by a thousand times and it shifts to 2399.5 cm −1 upon dimerization.…”

Section: Nbo Analysissupporting

confidence: 92%

“…The N-B bond distance in DBAB is still slightly shorter than that (1.665 Å) in H 3 NBH 3 . Dimerization generates novel H…H interactions with short contact distance (~2.0 Å), as has been observed experimentally in MBAB2 by VCD spectroscopy [17], and condenses the NB bond by~0.02 Å for all four monomers. The effect of dimerization on other geometrical parameters is slight.…”

Section: Resultssupporting

confidence: 58%

“…6). The E b of 8.8 kcal for MBAB2 has been predicted at the B3LYP/6-31G(d) level [17]. The decrease of E b along with the augmentation of substituent group number should be attributed to the steric effect.…”

Section: Nbo Analysismentioning

confidence: 87%

“…The main limitation is due to the signal contamination of DHB by other HB interactions in solution. The vibrational circular dichroism (VCD) and NMR spectroscopy are highly sensitive to conformational variations and environmental turbulence, and have thus been employed successfully to identify the DHB of chiral amine-borane complex [17].…”

Section: Introductionmentioning

confidence: 99%

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DFT investigation on dihydrogen-bonded amine-borane complexes

et al. 2015

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The DFT method has been employed in the exploration on dihydrogen-bonded amine-borane complexes, with a special emphasis on the dimerization and substituent group effect. Stable dihydrogen bonded complexes can be generated from these amine-borane monomers with the appearance of NH(δ+)…H(δ-)B interactions. The binding energy decreases gradually with the increase of the steric effect of the substituents. The substituent group number mainly varies the C-N bond length. The dimerization generates close H…H and influences predominantly the N-B distance. The effect of dimerization on IR and vibrational circular dichroism (VCD) spectra is stronger than that of the number of substituent groups, which leads to distinct NBO charge variation on α-C. Both the substituent group number and dimerization enhance the chemical shift difference between hydrogen atoms covalently bonded to N and B, Δδ H-H, which can be hired as an index for structural determination. It is proposed that amine-borane complexes with more substituent groups in higher degree of polymerization are potentially interesting materials for hydrogen storage. Graphical Abstract Both the number of substituent group and dimerization enhance the chemical shift difference of hydrogen atoms covalently bonded on N and B, Δδ H-H, which can be employed as an index for the structural determination.

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Section: Nbo Analysissupporting

confidence: 92%

Section: Resultssupporting

confidence: 58%

Section: Nbo Analysismentioning

confidence: 87%

Section: Introductionmentioning

confidence: 99%

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DFT investigation on dihydrogen-bonded amine-borane complexes

et al. 2015

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“…of little populated conformers. [11][12][13] Furthermore, VCD spectroscopy has been shown to be a very powerful technique to study intermolecular interactions such as solutesolvent [14][15][16][17] or solute-solute [18][19][20][21][22] interactions as well as chirality transfer phenomena. Slight warming of the solid matrix also enables the diffusion controlled generation of larger molecular clusters.…”

Section: Introductionmentioning

confidence: 99%

Conformational distortion of α-phenylethyl amine in cryogenic matrices – a matrix isolation VCD study

Pollok

Merten

2016

Phys. Chem. Chem. Phys.

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The chiral amine α-phenylethyl amine (PEA) was isolated in cryogenic matrices and investigated using vibrational circular dichroism (VCD) and infrared spectroscopy. The potential energy surface (PES) of PEA features five different conformers connected by relatively low conformational transition states. Based on the IR spectra, it could be confirmed that all conformational energy barriers are passed at a deposition temperature of 20 K, and that only the global minimum conformation of PEA is populated in both argon and nitrogen matrices. However, differences in the calculated and experimental VCD spectra indicate deviations from the minimum structure by perturbation of the phenyl ring as well as of the amine orientation. The degree of the perturbation is found to also depend on the choice of the host gas, which shows the subtle influence of the environment on the conformational distortion of PEA.

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Chiral Recognition by Molecular Spectroscopy

Pecul

Sadlej

2019

Molecular Spectroscopy

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Evidence of Dihydrogen Bonding of a Chiral Amine–Borane Complex in Solution by VCD Spectroscopy

Cited by 31 publications

References 43 publications

DFT investigation on dihydrogen-bonded amine-borane complexes

DFT investigation on dihydrogen-bonded amine-borane complexes

Conformational distortion of α-phenylethyl amine in cryogenic matrices – a matrix isolation VCD study

Chiral Recognition by Molecular Spectroscopy

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