Joshua D Queen1, Sini Irvankoski2, James C Fettinger1, Heikki M Tuononen2, Philip P Power1. 1. Department of Chemistry, University of California, Davis, One Shields Avenue, Davis California, 95616, United States. 2. Department of Chemistry, NanoScience Centre, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland.
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).
The reaction of :class="Chemical">AlAriPr8 (class="Chemical">pan class="Chemical">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 imideAriPr8AlNArMe6 (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 orbitalcomponents 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 Me3SiN3gave 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).
Authors: Matthew J Evans; Mathew D Anker; Claire L McMullin; Samuel E Neale; Nasir A Rajabi; Martyn P Coles Journal: Chem Sci Date: 2022-03-31 Impact factor: 9.969