A1 Journal article (refereed)
A Monomeric Aluminum Imide (Iminoalane) with Al–N Triple-Bonding : Bonding Analysis and Dispersion Energy Stabilization (2021)

Queen, J. D., Irvankoski, S., Fettinger, J. C., Tuononen, H. M., & Power, P. P. (2021). A Monomeric Aluminum Imide (Iminoalane) with Al–N Triple-Bonding : Bonding Analysis and Dispersion Energy Stabilization. Journal of the American Chemical Society, 143(17), 6351-6356. https://doi.org/10.1021/jacs.1c02463

JYU authors or editors

Irvankoski, Sini
Tuononen, Heikki

Publication details

All authors or editors: Queen, Joshua D.; Irvankoski, Sini; Fettinger, James C.; Tuononen, Heikki M.; Power, Philip P.

Journal or series: Journal of the American Chemical Society

ISSN: 0002-7863

eISSN: 1520-5126

Publication year: 2021

Publication date: 21/04/2021

Volume: 143

Issue number: 17

Pages range: 6351-6356

Publisher: American Chemical Society (ACS)

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/jacs.1c02463

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/76290

Abstract

The reaction of :AlAriPr8 (AriPr8 = C6H-2,6-(C6H2-2,4,6-iPr3)2-3,5-iPr2) with ArMe6N3 (ArMe6 = C6H3-2,6-(C6H2-2,4,6-Me3)2) in hexanes at ambient temperature gave the aluminum imide AriPr8AlNArMe6 (1). Its crystal structure displayed short Al–N distances of 1.625(4) and 1.628(3) Å with linear (C–Al–N–C = 180°) or almost linear (C–Al–N = 172.4(2)°; Al–N–C = 172.5(3)°) geometries. DFT calculations confirm linear geometry with an Al–N distance of 1.635 Å. According to energy decomposition analysis, the Al–N bond has three orbital components totaling −1350 kJ mol–1 and instantaneous interaction energy of −551 kJ mol–1 with respect to :AlAriPr8 and ArMe6N̈:. Dispersion accounts for −89 kJ mol–1, which is similar in strength to one Al–N π-interaction. The electronic spectrum has an intense transition at 290 nm which tails into the visible region. In the IR spectrum, the Al–N stretching band is calculated to appear at ca. 1100 cm–1. In contrast, reaction of :AlAriPr8 with 1-AdN3 or Me3SiN3 gave transient imides that immediately reacted with a second equivalent of the azide to give AriPr8Al[(NAd)2N2] (2) or AriPr8Al(N3){N(SiMe3)2} (3).

Keywords: chemical compounds; coordination complexes; aluminium

Fields of science: