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Tetraglymes as Prochiral Host Reagents for Ammonia Borane. / Shelyganov, Pavel A.; Virovets, Alexander; Peresypkina, Eugenia et al.

In: Zeitschrift fur Anorganische und Allgemeine Chemie, Vol. 645, No. 3, 15.02.2019, p. 317-322.

Research output: Contribution to journalArticlepeer-review

Harvard

Shelyganov, PA, Virovets, A, Peresypkina, E, Scheer, M & Timoshkin, AY 2019, 'Tetraglymes as Prochiral Host Reagents for Ammonia Borane', Zeitschrift fur Anorganische und Allgemeine Chemie, vol. 645, no. 3, pp. 317-322. https://doi.org/10.1002/zaac.201800333

APA

Shelyganov, P. A., Virovets, A., Peresypkina, E., Scheer, M., & Timoshkin, A. Y. (2019). Tetraglymes as Prochiral Host Reagents for Ammonia Borane. Zeitschrift fur Anorganische und Allgemeine Chemie, 645(3), 317-322. https://doi.org/10.1002/zaac.201800333

Vancouver

Shelyganov PA, Virovets A, Peresypkina E, Scheer M, Timoshkin AY. Tetraglymes as Prochiral Host Reagents for Ammonia Borane. Zeitschrift fur Anorganische und Allgemeine Chemie. 2019 Feb 15;645(3):317-322. doi: 10.1002/zaac.201800333

Author

Shelyganov, Pavel A. ; Virovets, Alexander ; Peresypkina, Eugenia et al. / Tetraglymes as Prochiral Host Reagents for Ammonia Borane. In: Zeitschrift fur Anorganische und Allgemeine Chemie. 2019 ; Vol. 645, No. 3. pp. 317-322.

BibTeX

@article{fa6bd92fcd954430bd1528ac135090e2,
title = "Tetraglymes as Prochiral Host Reagents for Ammonia Borane",
abstract = "The molecular structure of the complex of ammonia borane (AB) with acyclic ether tetraglyme Me(OCH2CH2)4OMe (1), 1·(AB)2 was determined by single-crystal X-ray structure analysis for the first time. The crystal structure features two AB molecules, bonded by dihydrogen bonds, per one tetraglyme unit. The intermolecular BH···HN distances of 1.94 {\AA} are shorter than those in the solid ammonia borane (2.02–2.32 {\AA}). A comparison of the hydrogen and dihydrogen bonds in 1·(AB)2 and in the complexes of AB with crown-ethers (CE) was carried out. The complex formation with both the CE and the acyclic polyether 1 activates the B–H bond in AB via N–H···O hydrogen bonds and therefore increases the reducing activity of AB. Supposedly, the structure of 1·(AB)2 is related to the initial steps of the AB activation in a polyether solution. The effect of the substituents on the complexation of the substituted derivatives of 1 comes down to a structural adjustment minimizing steric repulsion. Computations reveal that the complexation of diastereomeric disubstituted glymes with AB leads to the formation of diastereomeric complexes that differ noticeably in stability. This is a prerequisite for inducing stereoselectivity, which makes such complexes attractive for potential synthetic applications.",
keywords = "Ammonia borane, Chirality, Crown compounds, Density functional computations, Tetraglyme, CIS ISOMER, THERMOCHEMISTRY, COMPLEXES, CRYSTAL, SUPRAMOLECULAR STRUCTURES, 1-1 ADDUCT, HYDROGEN, KETONES, 2,3,11,12-TETRA-ANISYL-18-CROWN-6, METAL-FREE",
author = "Shelyganov, {Pavel A.} and Alexander Virovets and Eugenia Peresypkina and Manfred Scheer and Timoshkin, {Alexey Y.}",
note = "Publisher Copyright: {\textcopyright} 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",
year = "2019",
month = feb,
day = "15",
doi = "10.1002/zaac.201800333",
language = "English",
volume = "645",
pages = "317--322",
journal = "Zeitschrift fur Anorganische und Allgemeine Chemie",
issn = "0044-2313",
publisher = "Wiley-VCH Verlag",
number = "3",

}

RIS

TY - JOUR

T1 - Tetraglymes as Prochiral Host Reagents for Ammonia Borane

AU - Shelyganov, Pavel A.

AU - Virovets, Alexander

AU - Peresypkina, Eugenia

AU - Scheer, Manfred

AU - Timoshkin, Alexey Y.

N1 - Publisher Copyright: © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2019/2/15

Y1 - 2019/2/15

N2 - The molecular structure of the complex of ammonia borane (AB) with acyclic ether tetraglyme Me(OCH2CH2)4OMe (1), 1·(AB)2 was determined by single-crystal X-ray structure analysis for the first time. The crystal structure features two AB molecules, bonded by dihydrogen bonds, per one tetraglyme unit. The intermolecular BH···HN distances of 1.94 Å are shorter than those in the solid ammonia borane (2.02–2.32 Å). A comparison of the hydrogen and dihydrogen bonds in 1·(AB)2 and in the complexes of AB with crown-ethers (CE) was carried out. The complex formation with both the CE and the acyclic polyether 1 activates the B–H bond in AB via N–H···O hydrogen bonds and therefore increases the reducing activity of AB. Supposedly, the structure of 1·(AB)2 is related to the initial steps of the AB activation in a polyether solution. The effect of the substituents on the complexation of the substituted derivatives of 1 comes down to a structural adjustment minimizing steric repulsion. Computations reveal that the complexation of diastereomeric disubstituted glymes with AB leads to the formation of diastereomeric complexes that differ noticeably in stability. This is a prerequisite for inducing stereoselectivity, which makes such complexes attractive for potential synthetic applications.

AB - The molecular structure of the complex of ammonia borane (AB) with acyclic ether tetraglyme Me(OCH2CH2)4OMe (1), 1·(AB)2 was determined by single-crystal X-ray structure analysis for the first time. The crystal structure features two AB molecules, bonded by dihydrogen bonds, per one tetraglyme unit. The intermolecular BH···HN distances of 1.94 Å are shorter than those in the solid ammonia borane (2.02–2.32 Å). A comparison of the hydrogen and dihydrogen bonds in 1·(AB)2 and in the complexes of AB with crown-ethers (CE) was carried out. The complex formation with both the CE and the acyclic polyether 1 activates the B–H bond in AB via N–H···O hydrogen bonds and therefore increases the reducing activity of AB. Supposedly, the structure of 1·(AB)2 is related to the initial steps of the AB activation in a polyether solution. The effect of the substituents on the complexation of the substituted derivatives of 1 comes down to a structural adjustment minimizing steric repulsion. Computations reveal that the complexation of diastereomeric disubstituted glymes with AB leads to the formation of diastereomeric complexes that differ noticeably in stability. This is a prerequisite for inducing stereoselectivity, which makes such complexes attractive for potential synthetic applications.

KW - Ammonia borane

KW - Chirality

KW - Crown compounds

KW - Density functional computations

KW - Tetraglyme

KW - CIS ISOMER

KW - THERMOCHEMISTRY

KW - COMPLEXES

KW - CRYSTAL

KW - SUPRAMOLECULAR STRUCTURES

KW - 1-1 ADDUCT

KW - HYDROGEN

KW - KETONES

KW - 2,3,11,12-TETRA-ANISYL-18-CROWN-6

KW - METAL-FREE

UR - http://www.scopus.com/inward/record.url?scp=85054856930&partnerID=8YFLogxK

U2 - 10.1002/zaac.201800333

DO - 10.1002/zaac.201800333

M3 - Article

AN - SCOPUS:85054856930

VL - 645

SP - 317

EP - 322

JO - Zeitschrift fur Anorganische und Allgemeine Chemie

JF - Zeitschrift fur Anorganische und Allgemeine Chemie

SN - 0044-2313

IS - 3

ER -

ID: 17117239