Premium
Isomerism and Biradical Character of Tetrapnictide Dianions: A Computational Study
Author(s) -
Coburger Peter,
Wolf Robert,
Grützmacher Hansjörg
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000422
Subject(s) - chemistry , solvation , counterion , density functional theory , coupled cluster , reactivity (psychology) , computational chemistry , cluster (spacecraft) , planar , character (mathematics) , complete active space , electronic structure , square (algebra) , crystallography , ion , molecule , organic chemistry , medicine , alternative medicine , computer graphics (images) , geometry , pathology , basis set , computer science , mathematics , programming language
We present a computational study on tetrapnictide dianions Pn 4 2– (Pn = P, As, Sb, Bi), using density functional theory (DFT), coupled‐cluster [DLPNO‐CCSD(T)] and complete active space self‐consistent field (CASSCF) methods. Environmental effects such as solvation and coordination of counterions are included. The calculations reveal that out of three isomers (square‐planar, butterfly and capped‐triangle), the square planar isomers are generally the most stable. The counterion (Li + and Mg 2+ ) used in the calculations have a substantial effect on the relative stabilities. The square planar isomers show considerable biradical character. Calculated reactions toward alkenes indicate that this unusual electronic structure has significant implications on the reactivity of the Pn 4 2– dianions.