Open AccessIndium–Arsenic Molecules with an In≡As Triple Bond: A Theoretical Approach
Author(s) -
JiaSyun Lu,
Yang Mei,
MingDer Su
Publication year - 2017
Publication title -
acs omega
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.779
H-Index - 40
ISSN - 2470-1343
DOI - 10.1021/acsomega.7b00113
Subject(s) - chemistry , triple bond , intramolecular force , steric effects , molecule , carbene , density functional theory , computational chemistry , valence (chemistry) , potential energy surface , single bond , singlet state , crystallography , stereochemistry , double bond , atomic physics , physics , group (periodic table) , catalysis , organic chemistry , excited state
The effect of substitution on the potential energy surfaces of RIn≡AsR (R = F, OH, H, CH 3 , and SiH 3 and R' = SiMe(Si t Bu 3 ) 2 , Si i PrDis 2 , and N -heterocyclic carbene (NHC)) is determined using density functional theory calculations (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP, and B3LYP/LANL2DZ+dp). The computational studies demonstrate that all of the triply bonded RIn≡AsR species prefer to adopt a bent geometry, which is consistent with the valence electron model. The theoretical studies show that RIn≡AsR molecules that have smaller substituents are kinetically unstable with respect to their intramolecular rearrangements. However, triply bonded R'In≡AsR' species that have bulkier substituents (R' = SiMe(Si t Bu 3 ) 2 , Si i PrDis 2 , and NHC) occupy minima on the singlet potential energy surface, and they are both kinetically and thermodynamically stable. That is, the electronic and steric effects of bulky substituents play an important role in making molecules that feature an In≡As triple bond viable as a synthetic target. Moreover, two valence bond models are used to interpret the bonding character of the In≡As triple bond. One is model [A], which is best represented as . This interprets the bonding conditions for RIn≡AsR molecules that feature small ligands. The other is model [B], which is best represented as . This explains the bonding character of RIn≡PAsR molecules that feature large substituents.