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. Issue 3 (14th December 2015)

• Record Type: Journal Article
• Authors: Xie, Hujun; Liu, Chengcheng; Yuan, Ying; Zhou, Tao; Fan, Ting; Lei, Qunfang; Fang, Wenjun
• Is Part Of: Dalton transactions. Volume 45:Issue 3(2016)
• Page Start: 1152
• Page End: 1159
• Publication Date: 2015-12-14
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt03264d
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Frontier molecular orbital theory analysis indicates that N2 O is activated by nucleophilic attack by the phenyl or hydride ligand. Abstract : The mechanisms for the oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives (Cp* = η 5 -C5 Me5 ) 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 N2 O. The calculations showed that the complex with an initial O -coordination of N2 O to the coordinatively unsaturated Hf center is not a local minimum. Then we proposed a new reaction mechanism to investigate how N2 O is activated and why N2 O selectively oxidize phenyl and hydride ligands of . Frontier molecular orbital theory analysis indicates that N2 O is activated by nucleophilic attack by the phenyl or hydride ligand. Present calculations provide new insights into the activation of N2 O 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.