Electronic bond tuning with heterocyclic carbenes

Handle URI:
http://hdl.handle.net/10754/562494
Title:
Electronic bond tuning with heterocyclic carbenes
Authors:
Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Jacobsen, Heiko
Abstract:
We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Dalton Transactions
Issue Date:
2013
DOI:
10.1039/c3dt32923b
Type:
Article
ISSN:
14779226
Sponsors:
The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement no. CP-FP 211468-2 EUMET. L. C. thanks the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici, Italy.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorJacobsen, Heikoen
dc.date.accessioned2015-08-03T10:40:10Zen
dc.date.available2015-08-03T10:40:10Zen
dc.date.issued2013en
dc.identifier.issn14779226en
dc.identifier.doi10.1039/c3dt32923ben
dc.identifier.urihttp://hdl.handle.net/10754/562494en
dc.description.abstractWe discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.en
dc.description.sponsorshipThe research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement no. CP-FP 211468-2 EUMET. L. C. thanks the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici, Italy.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.titleElectronic bond tuning with heterocyclic carbenesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalDalton Transactionsen
dc.contributor.institutionDipartimento di Chimica e Biologia, Università di Salerno, Via Ponte don Melillo, 84084 Fisciano, Italyen
dc.contributor.institutionKemKom, 1215 Ursulines Ave., New Orleans, LA 70116, United Statesen
kaust.authorCavallo, Luigien
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.