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 -