Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

Handle URI:
http://hdl.handle.net/10754/562064
Title:
Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts
Authors:
Lamberti, Marina; Fortman, George C.; Poater, Albert; Broggi, Julie; Slawin, Alexandra M. Z.; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Nolan, Steven P.
Abstract:
The performance of 16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azidealkyne cycloaddition reactions that afford the 1,2,3- triazole products. The scope of the Cp*Ru(PiPr 3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were conducted and revealed a number of proposed intermediates. Cp*Ru- (PiPr3)(2-HCCPh)Cl was observed and characterized by 1H, 13C, and 31P NMR at temperatures between 273 and 213 K. A rare example of N,N-κ2-phosphazide complex, Cp*Ru(κ2- iPr3PN3Bn)Cl, was fully characterized, and a single-crystal X-ray diffraction structure was obtained. DFT calculations describe a complete map of the catalytic reactivity with phenylacetylene and/or benzylazide. © 2012 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society
Journal:
Organometallics
Issue Date:
23-Jan-2012
DOI:
10.1021/om2012425
Type:
Article
ISSN:
02767333
Sponsors:
S.P.N. would like to thank the ERC (Advanced Researcher Award FUNCAT) for financial support. A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (ref RYC-2009-05226) and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900). L.C. and A.P. thank the HPC team of Enea (www.enea.it) for using the ENEA-GRID and the HPC facilities CRESCO (www.cresco.enea.it) in Portici, Italy. M.L. acknowledges Salerno Province and the University of Salerno for supporting her stay at the University of St Andrews (International Mobility Scholarship 2009). S.P.N. is a Royal Society Wolfson Research Merit Award holder.
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.authorLamberti, Marinaen
dc.contributor.authorFortman, George C.en
dc.contributor.authorPoater, Alberten
dc.contributor.authorBroggi, Julieen
dc.contributor.authorSlawin, Alexandra M. Z.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorNolan, Steven P.en
dc.date.accessioned2015-08-03T09:43:54Zen
dc.date.available2015-08-03T09:43:54Zen
dc.date.issued2012-01-23en
dc.identifier.issn02767333en
dc.identifier.doi10.1021/om2012425en
dc.identifier.urihttp://hdl.handle.net/10754/562064en
dc.description.abstractThe performance of 16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azidealkyne cycloaddition reactions that afford the 1,2,3- triazole products. The scope of the Cp*Ru(PiPr 3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were conducted and revealed a number of proposed intermediates. Cp*Ru- (PiPr3)(2-HCCPh)Cl was observed and characterized by 1H, 13C, and 31P NMR at temperatures between 273 and 213 K. A rare example of N,N-κ2-phosphazide complex, Cp*Ru(κ2- iPr3PN3Bn)Cl, was fully characterized, and a single-crystal X-ray diffraction structure was obtained. DFT calculations describe a complete map of the catalytic reactivity with phenylacetylene and/or benzylazide. © 2012 American Chemical Society.en
dc.description.sponsorshipS.P.N. would like to thank the ERC (Advanced Researcher Award FUNCAT) for financial support. A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (ref RYC-2009-05226) and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900). L.C. and A.P. thank the HPC team of Enea (www.enea.it) for using the ENEA-GRID and the HPC facilities CRESCO (www.cresco.enea.it) in Portici, Italy. M.L. acknowledges Salerno Province and the University of Salerno for supporting her stay at the University of St Andrews (International Mobility Scholarship 2009). S.P.N. is a Royal Society Wolfson Research Merit Award holder.en
dc.publisherAmerican Chemical Societyen
dc.titleCoordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalystsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalOrganometallicsen
dc.contributor.institutionEaStCHEM School of Chemistry, University of St Andrews, St Andrews, KY16 9ST, United Kingdomen
dc.contributor.institutionDipartimento di Chimica e Biologia, Università di Salerno, Via Ponte Don Melillo, I-84084 Fisciano (SA), Italyen
dc.contributor.institutionCatalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park of the University of Girona, Emili Grahit 101, E-17003 Girona, Spainen
dc.contributor.institutionInstitut de Química Computacional, Departament de Química, Universitat de Girona, E-17071 Girona, Spainen
kaust.authorCavallo, Luigien
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.