NDLI: Lewis base complexes of $AlH_{3}:$ structural determination of monomeric and polymeric adducts by X-ray crystallography and DFT calculations

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Decken, Andreas Mcgrady, G. Sean Humphries, Terry D. Munroe, Keelie T.
Description	Author Affiliation: Humphries TD ( Department of Chemistry, University of New Brunswick, P.O. Box 4400, Fredericton, NB E3B 5A3, Canada. smcgrady@unb.ca)
Abstract	The $AlH_{3}$ adducts of TMEDA $(Me_{2}NCH_{2}CH_{2}NMe_{2}),$ DIOX $(O(CH_{2}CH_{2})_{2}O),$ TEA $(Et_{3}N),$ BDMA $(PhNMe_{2}),$ and TMPDA $(Me_{2}NCH_{2}CH_{2}CH_{2}NMe_{2})$ have each been characterised by single-crystal X-ray diffraction at low temperature, by $^{1}H,$ $^{14}N$ and $^{27}Al$ NMR and FT-Raman and FT-IR spectroscopy , and by DFT calculations and elemental analysis . Hence, $AlH_{3}·TMEDA$ and $AlH_{3}·DIOX$ are both shown to adopt a polymeric structure, with the bidentate ligand bridging two Al centres, each of which adopts a trigonal bipyramidal (TBP) arrangement with equatorial hydride moieties. The 1:2 adduct $AlH_{3}·2BDMA$ is monomeric but the geometry at the Al centre resembles closely that of the polymeric TMEDA and DIOX complexes. $AlH_{3}·TEA$ alone adopts a monomeric structure in which the Al centre is tetrahedrally coordinated by three hydride and one amine ligand . The Al–L bond distance of 2.0240(17) Å for $AlH_{3}·TEA$ is the shortest of all the complexes in this study, and $AlH_{3}·TEA$ also possesses the shortest Al–H bonds. $AlH_{3}·DIOX$ has the shortest Al–L bond distance of the polymeric species (2.107(14) Å) on account of the higher electronegativity of the oxygen donor. The structure of $AlH_{3}·TMEDA$ was determined at low temperature (monoclinic space group $P2_{1}/c),$ and salient features are compared to the previous room temperature study, for which a highly disordered orthorhombic space group $(P2_{1}2_{1}2_{1})$ was reported. The polymeric structures appear to be stabilised by a number of intermolecular interactions and unconventional hydrogen bonds; these are most pronounced for $AlH_{3}·DIOX,$ whose chains are connected by highly directional C–H⋯H–Al bonding with an H⋯H distance of 2.32(6) Å.
ISSN	14779226
Issue Number	19
Journal	Dalton Trans.
Volume Number	42
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-05-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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