Computational insight into asymmetric uranyl‐salophen coordinated with α, β‐unsaturated aldehydes and ketones

• Published in: Applied organometallic chemistry 2018-03, Vol.32 (3), p.n/a
• Main Authors: Lan, Wen‐Bo, Wang, Xiao‐Feng, He, Li‐Ping, Meng, Yan‐Bin, Li, Jun, Qiu, Bin, Nie, Chang‐Ming
• Format: Article
• Language: English
• Subjects: Aldehydes; asymmetric uranyl‐salophen; Asymmetry; Benzene; Catalysis; Catalytic activity; Chemistry; coordination; Density functional theory; Ketones; β‐unsaturated aldehydes and ketones
• ISSN: 0268-2605; 1099-0739
• DOI: 10.1002/aoc.4137

The study of the catalytic activity and activation mechanism of asymmetric uranyl‐salophens with α, β‐unsaturated aldehydes or α, β‐unsaturated ketones, is a research hotspot. In this paper, the complexes of the uranyl–salophen(U‐S) modified by unilateral benzene, coordinated with cyclohexenone, cyclopentenone and acrolein, were investigated using density functional theory calculations at the level of B3LYP/6‐311G(d, p) basis set. The results showed that the uranyl‐salophen(U‐S) weakened the large π bond between C = C and C = O of the α, β‐unsaturated aldehydes and ketones, making the unsaturated aldehydes and ketones activated. In addition, the molecular‐recognition selectivity of the asymmetrical uranyl‐salophen for cyclohexenone and cyclopentenone were much higher than for acrolein. The asymmetrical uranyl‐salophen have the molecular‐recognition selectivity for the α, β‐unsaturated aldehydes and ketones and could weaken the large the π bond between C = C and C = O of the α, β‐unsaturated aldehydes and ketones.