Molecular structure of diethylaminoalane in the solid state: an X-ray powder diffraction, DFT calculation and Raman spectroscopy study

Abstract

The crystal structure of diethylaminoalane, [H2Al-N(C2H5)2]2, was determined by X-ray powder diffraction in conjunction with DFT calculations. Diethylaminoalane crystallizes in the monoclinic space group P21/c with a = 7.4020 (2), b = 12.9663 (3), c = 7.2878 (2) Å and β = 90.660 (2)° at 293 K. The crystal structure was confirmed by DFT calculations and Raman spectroscopy. The molecular structure of diethylaminoalane consists of dimers of [H2Al-N(CH2CH3)2] in which an Al2N2 four-membered ring is formed by a center of inversion. Such an arrangement of the aminoalane moieties in the crystal structure is well known for this class of compound, as shown by the comparison with ethylmethylaminoalane and diisopropylaminoalane.

Molecular Main Group Metal Hydrides

“…As with carbon-supported aluminum hydride systems, a common reactivity pathway is the hydroalumination of organic π-bonds. Given the plethora of new N -donor aluminum hydride systems reported in the past two decades, ,− this section will aim to focus on the new bonding motifs and reactivity pathways uncovered in this area.…”

The plastic crystalline A15 phase of dimethylaminoalane, [N(CH3)2–AlH2]3

“…This journal is © The Royal Society of Chemistry 2016 a four-membered ring character. 24,25 Indeed, both the 15 N and 27 Al signals of the dimers match the low-field shifted signal of the minor component (Table S1, ESI †). Furthermore, using a stimulated echo for the measurement of the diffusion coefficient it was possible to show that the minor component behaves like a smaller species of the major component (Fig.…”

Direct Hydrogenation of Aluminum via Stabilization with Triethylenediamine: A Mechanochemical Approach to Synthesize the Triethylenediamine ⋅ AlH3 Adduct

“…The utilization of primary and secondary amines produces oligomerized products by hydrogen release, e.g. [Me 2 N−AlH 2 ] 3 , [Et 2 N−AlH 2 ] 2 , [ i PrN−AlH] 6 , or [ t BuN−AlH] 4 , which are limited regarding their rehydrogenation via ring‐opening. In contrast, release of H 2 at simultaneous oligomerization of alane adducts with tertiary amines, e.g.…”