Juuso Valjus, Heikki M. Tuononen, Risto S. Laitinen, Tristram Chivers, Computational investigations of 18-electron triatomic sulfur–nitrogen anions, Canadian Journal of Chemistry, 2018, 96:591-598, https://doi.org/10.1139/cjc-2018-0047
Computational investigations of 18-electron triatomic sulfur–nitrogen anions
|Author:||Valjus, Juuso1; Tuononen, Heikki M.1; Laitinen, Risto S.2;|
1Department of Chemistry, Nanoscience Centre, P.O. Box 35, FI-40014 University of Jyväskylä, Finland
2Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, P.O. Box 3000, FI-90014 University of Oulu, Finland
3Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB T2N 1N4, Canada
|Online Access:||PDF Full Text (PDF, 2.5 MB)|
|Persistent link:|| http://urn.fi/urn:nbn:fi-fe202001212906
Canadian Science Publishing,
|Publish Date:|| 2020-01-21
MRCI-SD/def2-QZVP and PBE0/def2-QZVP calculations have been employed for the analysis of geometries, stabilities, and bonding of isomers of the 18-electron anions N₂S²⁻, NS₂⁻, and NSO⁻. Isomers of the isoelectronic neutral molecules SO₂, S₂O, S₃, and O₃ are included for comparison. The sulfur-centered acyclic NSN2⁻, NSS⁻, and NSO⁻ anions are the most stable isomers of their respective molecular compositions. However, the nitrogen-centered isomers SNS⁻ and SNO⁻ lie close enough in energy to their more stable counterparts to allow their occurrence. The experimental structural information, where available, is in good agreement with the optimized bond parameters. The bonding in all investigated species is qualitatively similar, though electron density analyses reveal important quantitative differences that arise from bond polarization. Most of the investigated systems can be described with a single configuration wave function, the two notable exceptions being isomers SSS and OOO that show some diradical character. The computed MRCI-SD/def2-QZVP absorption maxima for SNS⁻ and NSS⁻ are 342 and 327 nm, respectively. The corresponding PBE0/def2-QZVP values in acetonitrile are 353 and 333 nm. These data support the proposed initial formation of SNS⁻ from electrochemical or chemical reduction of SSNS⁻ based on experimental UV–vis spectra. The interconversion of SNS⁻ and NSS⁻ is calculated to be facile and reversible, leading to an equilibrium mixture that also includes the remarkably stable dianion SNSNSS²⁻. Thus, salts of either SNS⁻ or NSS⁻ with bulky organic cations represent feasible synthetic targets.
Canadian journal of chemistry
|Pages:||591 - 598|
|Type of Publication:||
A1 Journal article – refereed
|Field of Science:||
116 Chemical sciences
Financial support from the University of Jyväskylä (H.M.T and J.V.) and the Natural Sciences and Engineering Research Council of Canada (T.C.) is gratefully acknowledged.
© 2018 Canadian Science Publishing. The final authenticated version is available online at https://doi.org/10.1139/cjc-2018-0047.