ISSN:
1434-1948
Keywords:
Aminoalanes
;
Alanes
;
Ab initio calculations
;
27Al-NMR spectroscopy
;
Structure elucidation
;
Substituent effects
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reactions of metallated nucleophiles MIY [Y = OR, SR, NR2, PR2, AsR2, CR3, Si(SiMe3)3, R = organyl, H] with bis(2,2,6,6-tetramethylpiperidino)aluminum halides [tmp2AlX, (X = Cl, Br, I)] offer facile access to a variety of bis(amino)alanes of the type tmp2AlY. As indicated by 27Al-NMR spectroscopy, mass spectrometry and X-ray crystal structure determina-tions, all of these compounds are monomeric in the solid state, in solution, and in the gas phase. Even Al-E single bonds (E = Si, P, As etc.) that are not commonly encountered are stabilized by the supporting tmp fragments. The results of a systematic analysis of the bonding parameters determined for the tmp2AlY compounds, combined with a quantum mechanical study on model compounds (H2N)2AlY, not only reveal the presence of a highly polar Al-N bond, but at the same time rule out AlN-pp(π) bonding, in contrast to the situation in the analogous tmp2BY compounds. It is shown that the Al-N bond length depends on the acidic character of the protic species HY: the shorter d(Al-N), the less basic is Y.
Type of Medium:
Electronic Resource
