Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

Marina Lamberti; George C. Fortman; Albert Poater; Julie Broggi; Alexandra M. Z. Slawin; Luigi Cavallo; Steven P. Nolan

doi:10.1021/om2012425

Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

Marina Lamberti, George C. Fortman, Albert Poater, Julie Broggi, Alexandra M. Z. Slawin, Luigi Cavallo, Steven P. Nolan

Research output: Contribution to journal › Article › peer-review

74 Scopus citations

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.

Original language	English (US)
Pages (from-to)	756-767
Number of pages	12
Journal	Organometallics
Volume	31
Issue number	2
DOIs	https://doi.org/10.1021/om2012425
State	Published - Jan 10 2012

ASJC Scopus subject areas

Organic Chemistry
Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/om2012425

Cite this

@article{9fe6924376a240e0a9e2f4a91941a323,

title = "Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts",

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. {\textcopyright} 2012 American Chemical Society.",

author = "Marina Lamberti and Fortman, {George C.} and Albert Poater and Julie Broggi and Slawin, {Alexandra M. Z.} and Luigi Cavallo and Nolan, {Steven P.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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.",

year = "2012",

month = jan,

day = "10",

doi = "10.1021/om2012425",

language = "English (US)",

volume = "31",

pages = "756--767",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

AU - Lamberti, Marina

AU - Fortman, George C.

AU - Poater, Albert

AU - Broggi, Julie

AU - Slawin, Alexandra M. Z.

AU - Cavallo, Luigi

AU - Nolan, Steven P.

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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.

PY - 2012/1/10

Y1 - 2012/1/10

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/562064

UR - https://pubs.acs.org/doi/10.1021/om2012425

UR - http://www.scopus.com/inward/record.url?scp=84856911606&partnerID=8YFLogxK

U2 - 10.1021/om2012425

DO - 10.1021/om2012425

M3 - Article

SN - 0276-7333

VL - 31

SP - 756

EP - 767

JO - Organometallics

JF - Organometallics

IS - 2

ER -

Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

CCDC 820903: Experimental Crystal Structure Determination : (eta^5^-pentamethylcyclopentadienyl)-(1-benzyl-3-[tri(propan-2-yl)-phosphanylidene]triaz-1-ene)-chloro-ruthenium

Cite this

Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 820903: Experimental Crystal Structure Determination : (eta^5^-pentamethylcyclopentadienyl)-(1-benzyl-3-[tri(propan-2-yl)-phosphanylidene]triaz-1-ene)-chloro-ruthenium

Cite this