Reactions of Laser-Ablated Aluminum Atoms with Cyanogen: Matrix Infrared Spectra and Electronic Structure Calculations for Aluminum Isocyanides Al(NC)1,2,3 and Their Novel Dimers

The Journal of Physical Chemistry. a
Lester AndrewsYu Gong

Abstract

Laser-ablated Al atoms react with (CN)2 in excess argon during condensation at 4 K to produce AlNC, Al(NC)2, and Al(NC)3, which were computed (B3LYP) to be 27, 16, and 28 kJ/mol lower in energy, respectively, than their cyanide counterparts. Irradiation at 220-580 nm increased absorptions for the above molecules and the very stable Al(NC)4- anion. Annealing to 30, 35, and 40 K allowed for diffusion and reaction of trapped species and produced new bands for the Al(NC)1,2,3 dimers including a rhombic ring core (C)(AlN)2(C) with C's attached to the N's, a (NC)2Al(II)-Al(II)(NC)2 dimer with a computed Al-Al length of 2.557 Å, and the dibridged Al2(NC)6 molecule with a calculated D2 h structure and rhombic ring core like Al2H6. In contrast, the Al(NC)4- anion was destroyed on annealing presumably due to neutralization by Al+. B3LYP calculations also show that aluminum chlorides form the analogous molecules and dimers. In our search for possible new products, we calculated Al(NC)4 and found it to be a stable molecule, but it was not detected here.

References

Mar 29, 2003·Science·Lester Andrews, Xuefeng Wang
Sep 2, 2003·Angewandte Chemie·Norbert W Mitzel
Sep 17, 2004·Journal of the American Chemical Society·Xuefeng WangMario E Fajardo
Mar 17, 2006·The Journal of Physical Chemistry. a·Han-Gook Cho, Lester Andrews
Mar 29, 2007·The Journal of Physical Chemistry. a·Xuefeng Wang, Lester Andrews
Jul 7, 2007·The Journal of Chemical Physics·Marilyn E Jacox, Warren E Thompson
Nov 3, 2007·Inorganic Chemistry·Eric Rivard, Philip P Power
Mar 14, 2013·Journal of Computational Chemistry·Eric D GlendeningFrank Weinhold
Feb 10, 2017·Chemical Communications : Chem Comm·Bin LiHerbert W Roesky
Apr 4, 2017·Chemistry : a European Journal·Ralf HaigesKarl O Christe
Nov 3, 2017·The Journal of Physical Chemistry. a·Xiuting ChenYu Gong

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Citations

Dec 6, 2019·Angewandte Chemie·Lester Andrews, Han-Gook Cho
Aug 14, 2018·The Journal of Physical Chemistry. a·Xiuting ChenYu Gong
Aug 15, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Hongmin LiSebastian Riedel
Aug 24, 2019·The Journal of Physical Chemistry. a·Zongtang FangDavid A Dixon

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