Synthesis and characterization of gold(I) complexes of dibenzotropylidene-functionalized NHC ligands (Trop-NHCs)

Marcel Brill; Alba Collado-Martinez; David Bradford Cordes; Alexandra Martha Zoya Slawin; Matthias Vogt; Hansjoerg Gruetzmacher; Steven Patrick Nolan

doi:10.1021/om501093s

Synthesis and characterization of gold(I) complexes of dibenzotropylidene-functionalized NHC ligands (Trop-NHCs)

Marcel Brill, Alba Collado-Martinez, David Bradford Cordes, Alexandra Martha Zoya Slawin, Matthias Vogt, Hansjoerg Gruetzmacher, Steven Patrick Nolan

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

Abstract

Gold(I) complexes of dibenzotropylidene-functionalized N-heterocyclic carbene ligands (Trop-NHCs) have been prepared in order to investigate their structural features and to reveal possible interactions of the olefin unit with the metal center. The precursor imidazolium chloride salts (R-1) were generated in a single step using N-substituted imidazoles (R = H, Me, DiPP, Ad) and 1 or 2 equiv of Trop-Cl, generating unsymmetrical and symmetrical NHC-olefin hybrids. The structural parameters of the ligands were determined by synthesis and X-ray diffraction analysis of their corresponding gold(I) chloride complexes, revealing highly flexible steric demands of the Trop unit. Conversion of these complexes with halide-abstracting reagents such as AgNTf₂ and NaBArF₂₄ cleanly gave neutral, NTf₂-coordinated complexes of the type [(NHC)Au(NTf₂)] (R-3) and the cationic bis-NHC-coordinated complexes [(NHC)₂Au]BArF₂₄ (R-4), respectively. The Gagosz-type complexes R-3 were further tested in the hydration of diphenylacetylene, showing a clear trend in activity depending on the ligand’s sensitivity to hydrolysis.

Original language	English
Pages (from-to)	263-274
Number of pages	12
Journal	Organometallics
Volume	34
Issue number	1
Early online date	22 Dec 2014
DOIs	https://doi.org/10.1021/om501093s
Publication status	Published - 12 Jan 2015

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This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © 2014 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/om501093s
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@article{360c48964738456395f2a102a6d5a161,

title = "Synthesis and characterization of gold(I) complexes of dibenzotropylidene-functionalized NHC ligands (Trop-NHCs)",

abstract = "Gold(I) complexes of dibenzotropylidene-functionalized N-heterocyclic carbene ligands (Trop-NHCs) have been prepared in order to investigate their structural features and to reveal possible interactions of the olefin unit with the metal center. The precursor imidazolium chloride salts (R-1) were generated in a single step using N-substituted imidazoles (R = H, Me, DiPP, Ad) and 1 or 2 equiv of Trop-Cl, generating unsymmetrical and symmetrical NHC-olefin hybrids. The structural parameters of the ligands were determined by synthesis and X-ray diffraction analysis of their corresponding gold(I) chloride complexes, revealing highly flexible steric demands of the Trop unit. Conversion of these complexes with halide-abstracting reagents such as AgNTf2 and NaBArF24 cleanly gave neutral, NTf2-coordinated complexes of the type [(NHC)Au(NTf2)] (R-3) and the cationic bis-NHC-coordinated complexes [(NHC)2Au]BArF24 (R-4), respectively. The Gagosz-type complexes R-3 were further tested in the hydration of diphenylacetylene, showing a clear trend in activity depending on the ligand{\textquoteright}s sensitivity to hydrolysis.",

author = "Marcel Brill and Alba Collado-Martinez and Cordes, {David Bradford} and Slawin, {Alexandra Martha Zoya} and Matthias Vogt and Hansjoerg Gruetzmacher and Nolan, {Steven Patrick}",

note = "The ERC (Advanced Investigator Award-FUNCAT), Syngenta, and the EPSRC are gratefully thanked for support of this work. S.P.N. is a Royal Society Wolfson Research Merit Award holder.",

year = "2015",

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day = "12",

doi = "10.1021/om501093s",

language = "English",

volume = "34",

pages = "263--274",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society (ACS)",

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TY - JOUR

T1 - Synthesis and characterization of gold(I) complexes of dibenzotropylidene-functionalized NHC ligands (Trop-NHCs)

AU - Brill, Marcel

AU - Collado-Martinez, Alba

AU - Cordes, David Bradford

AU - Slawin, Alexandra Martha Zoya

AU - Vogt, Matthias

AU - Gruetzmacher, Hansjoerg

AU - Nolan, Steven Patrick

N1 - The ERC (Advanced Investigator Award-FUNCAT), Syngenta, and the EPSRC are gratefully thanked for support of this work. S.P.N. is a Royal Society Wolfson Research Merit Award holder.

PY - 2015/1/12

Y1 - 2015/1/12

N2 - Gold(I) complexes of dibenzotropylidene-functionalized N-heterocyclic carbene ligands (Trop-NHCs) have been prepared in order to investigate their structural features and to reveal possible interactions of the olefin unit with the metal center. The precursor imidazolium chloride salts (R-1) were generated in a single step using N-substituted imidazoles (R = H, Me, DiPP, Ad) and 1 or 2 equiv of Trop-Cl, generating unsymmetrical and symmetrical NHC-olefin hybrids. The structural parameters of the ligands were determined by synthesis and X-ray diffraction analysis of their corresponding gold(I) chloride complexes, revealing highly flexible steric demands of the Trop unit. Conversion of these complexes with halide-abstracting reagents such as AgNTf2 and NaBArF24 cleanly gave neutral, NTf2-coordinated complexes of the type [(NHC)Au(NTf2)] (R-3) and the cationic bis-NHC-coordinated complexes [(NHC)2Au]BArF24 (R-4), respectively. The Gagosz-type complexes R-3 were further tested in the hydration of diphenylacetylene, showing a clear trend in activity depending on the ligand’s sensitivity to hydrolysis.

AB - Gold(I) complexes of dibenzotropylidene-functionalized N-heterocyclic carbene ligands (Trop-NHCs) have been prepared in order to investigate their structural features and to reveal possible interactions of the olefin unit with the metal center. The precursor imidazolium chloride salts (R-1) were generated in a single step using N-substituted imidazoles (R = H, Me, DiPP, Ad) and 1 or 2 equiv of Trop-Cl, generating unsymmetrical and symmetrical NHC-olefin hybrids. The structural parameters of the ligands were determined by synthesis and X-ray diffraction analysis of their corresponding gold(I) chloride complexes, revealing highly flexible steric demands of the Trop unit. Conversion of these complexes with halide-abstracting reagents such as AgNTf2 and NaBArF24 cleanly gave neutral, NTf2-coordinated complexes of the type [(NHC)Au(NTf2)] (R-3) and the cationic bis-NHC-coordinated complexes [(NHC)2Au]BArF24 (R-4), respectively. The Gagosz-type complexes R-3 were further tested in the hydration of diphenylacetylene, showing a clear trend in activity depending on the ligand’s sensitivity to hydrolysis.

UR - http://pubs.acs.org/doi/suppl/10.1021/om501093s

U2 - 10.1021/om501093s

DO - 10.1021/om501093s

M3 - Article

SN - 0276-7333

VL - 34

SP - 263

EP - 274

JO - Organometallics

JF - Organometallics

IS - 1

ER -

Synthesis and characterization of gold(I) complexes of dibenzotropylidene-functionalized NHC ligands (Trop-NHCs)

Abstract

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