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• W2958403711 abstract "Abstract Following our recent steric studies on diaminocarbenes, here, electronic effects of symmetric acyclic, cyclic saturated, and cyclic unsaturated 2,4‐disubstituted structures ( 1 X , 3 X , and 5 X , respectively) are compared with their asymmetric corresponding 2,5‐disubstituted isomers ( 2 X , 4 X , and 6 X , respectively), at B3LYP/6‐311++G** level of theory (X = NH 2 , OH, OMe, SH, Ph, CN, CF 3 , NO 2 ). Both symmetric and asymmetric species ( 1 X ‐ 6 X ) appear with singlet(s) ground states. These are suggested by the conductor‐like polarizable continuum model (CPCM) on both gas‐phase and solvent‐phase optimized structures. Regardless of X, singlet‐triplet energy gap (Δ E S‐T ) and band gap (Δ E H‐L ) increase in going from acyclic to cyclic saturated and cyclic unsaturated structures (except 6 X ). More importantly, nucleophilicity ( N ) decreases (while electrophilicity, ω , increases) in going from acyclic to cyclic saturated and cyclic unsaturated structures for both symmetric and asymmetric carbenes. Acyclic 1 X and 2 X appear less stable than their corresponding cyclic 3 X and 6 X in the presence of either electron‐withdrawing or electron‐releasing substituents. The proton affinity (PA) increases in going from acyclic to cyclic saturated, while decreases in going to cyclic unsaturated structures for both symmetric and asymmetric carbenes. The calculated metal‐ligand isodesmic complexation energies, Δ E com , indicate that 1 X ‐6 X complexes have very strong M─(carbene) bonds. The trend of Δ E com for symmetric series is 1 X > 3 X > 5 X , while that for asymmetric appears as 6 X > 2 X > 4 X . Atoms in molecules (AIM) wavefunction analysis shows internal hydrogen bondings for 1 OH , 1 OMe , 1 CF3 , 2 Ph , and 4 NO2 . Hammett assessments are made on sensitivity of thermodynamic parameters of 1 X to 6 X toward electronic effects. Finally, basicity increases as a function of the carbenic bond angle for 1 X to 6 X . Hence, basicity increases in going from the unsaturated 5 X and 6 X (96°) to the saturated 3 X and 4 X (102°) and lastly to acyclic 1 X and 2 X (120°)." @default.
• W2958403711 created "2019-07-23" @default.
• W2958403711 creator A5003661533 @default.
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• W2958403711 date "2019-07-11" @default.
• W2958403711 modified "2023-10-10" @default.
• W2958403711 title "Electronic effects on diaminocarbenes: a theoretical quest" @default.
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• W2958403711 doi "https://doi.org/10.1002/poc.3996" @default.
• W2958403711 hasPublicationYear "2019" @default.
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