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Interaction of the [GaH 4 ] − Anion with Weak XH Acids − A Spectroscopic and Theoretical Study
Author(s) -
Belkova Natalia V.,
Filippov Oleg A.,
Filin Andrey M.,
Teplitskaya Liliya N.,
Shmyrova Yulia V.,
Gavrilenko Vyacheslav V.,
Golubinskaya Ludmila M.,
Bregadze Vladimir I.,
Epstein Lina M.,
Shubina Elena S.
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400084
Subject(s) - chemistry , denticity , crystallography , infrared spectroscopy , hydride , stereochemistry , crystal structure , metal , organic chemistry
The dihydrogen bonding (DHB) between the hydride atom of the [Bu 4 N][GaH 4 ] salt and different XH acids, namely CF 3 CH 2 OH, FCH 2 CH 2 OH, i PrOH, MeOH, indole and 4‐O 2 NC 6 H 4 NH 2 , has been investigated for the first time by low‐temperature IR spectroscopy. The DHB spectroscopic and thermodynamic parameters in solvents of low polarity and high basicity ( E j = 1.37) were obtained. The nature, structures, energies and electron distributions of the model DHB complexes of GaH 4 − with H 2 O, MeOH, CF 3 OH, H 2 NCF 3 or NO 2 C 6 H 4 NH 2 were studied by DFT calculations and compared with those of the analogous complexes of BH 4 − with H 2 O, MeOH or CF 3 OH. Two types of DHB structures with monodentate and symmetric chelate coordination were found. The lengthening of the X−H and Ga−H bonds, electron polarization and overlap population of the H ··· H bond are greater in the first type of structure. A comparative analysis of experimental data demonstrates that the spectroscopic and thermodynamic characteristics, e.g. ν(XH) and ν(GaH) band shifts, ν(XH) bonded integral intensities, formation enthalpies and E j of all the DHB complexes increase down the group (BH 4 − ·HX < GaH 4 − ·HX). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)