title: Oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives by nitrous oxide via selective oxygen atom transfer reactions: insights from quantum chemistry calculations.
abstract: The mechanisms for the oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives (Cp* = η(5)-C5Me5) by nitrous oxide via selective oxygen atom transfer reactions have been systematically studied by means of density functional theory (DFT) calculations. On the basis of the calculations, we investigated the original mechanism proposed by Hillhouse and co-workers for the activation of N2O. The calculations showed that the complex with an initial O-coordination of N2O to the coordinatively unsaturated Hf center is not a local minimum. Then we proposed a new reaction mechanism to investigate how N2O is activated and why N2O selectively oxidize phenyl and hydride ligands of . Frontier molecular orbital theory analysis indicates that N2O is activated by nucleophilic attack by the phenyl or hydride ligand. Present calculations provide new insights into the activation of N2O involving the direct oxygen atom transfer from nitrous oxide to metal-ligand bonds instead of the generally observed oxygen abstraction reaction to generate metal-oxo species.
authors.affiliation: Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018, People's Republic of China. hujunxie@gmail.com.
authors.forename: Hujun
authors.initials: H
authors.lastname: Xie
authors.affiliation: Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018, People's Republic of China. hujunxie@gmail.com.
authors.forename: Chengcheng
authors.initials: C
authors.lastname: Liu
authors.affiliation: Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018, People's Republic of China. hujunxie@gmail.com.
authors.forename: Ying
authors.initials: Y
authors.lastname: Yuan
authors.affiliation: Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018, People's Republic of China. hujunxie@gmail.com.
authors.forename: Tao
authors.initials: T
authors.lastname: Zhou
authors.affiliation: Division of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of Technology, SE-10044 Stockholm, Sweden. tingf@kth.se.
authors.forename: Ting
authors.initials: T
authors.lastname: Fan
authors.affiliation: Department of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China.
authors.forename: Qunfang
authors.initials: Q
authors.lastname: Lei
authors.affiliation: Department of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China.
authors.forename: Wenjun
authors.initials: W
authors.lastname: Fang