Change search
ReferencesLink to record
Permanent link

Direct link
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
Show others and affiliations
2016 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 45, no 3, 1152-1159 p.Article in journal (Refereed) PublishedText
Abstract [en]

The mechanisms for the oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives (Cp∗ = η5-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.

Place, publisher, year, edition, pages
2016. Vol. 45, no 3, 1152-1159 p.
Keyword [en]
N BOND-CLEAVAGE, MAIN-GROUP THERMOCHEMISTRY, METAL-CARBON BONDS, ELECTRON-TRANSFER, 1, 3-DIPOLAR CYCLOADDITIONS, NONCOVALENT INTERACTIONS, ORGANOMETALLIC OXIDES, CATALYTIC-REDUCTION, CRYSTAL-STRUCTURE, OXO COMPLEXES
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-181470DOI: 10.1039/c5dt03264dISI: 000367614700036PubMedID: 26660046ScopusID: 2-s2.0-84953932029OAI: oai:DiVA.org:kth-181470DiVA: diva2:899679
Note

QC 20160202. QC 20160205

Available from: 2016-02-02 Created: 2016-02-02 Last updated: 2016-02-05Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textPubMedScopus

Search in DiVA

By author/editor
Fan, Ting
By organisation
Theoretical Chemistry and Biology
In the same journal
Dalton Transactions
Theoretical Chemistry

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 19 hits
ReferencesLink to record
Permanent link

Direct link