Synthesis of AuI- and AuIII-bis(NHC) complexes: ligand influence on oxidative addition to AuI species

Alba Collado-Martinez; Jan Bohnenberger; María-José Oliva-Madrid; Pierrick Nun; David B. Cordes; Alexandra M. Z. Slawin; Steven P. Nolan

doi:10.1002/ejic.201600791

Synthesis of Au^I- and Au^III-bis(NHC) complexes: ligand influence on oxidative addition to Au^Ispecies

Alba Collado-Martinez, Jan Bohnenberger, María-José Oliva-Madrid, Pierrick Nun, David B. Cordes, Alexandra M. Z. Slawin, Steven P. Nolan

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

Abstract

The oxidation chemistry of a range of Au^I-bis(NHC) (NHC = N-heterocyclic carbene) complexes with hypervalent iodine(III) oxidants has been explored. Au^I-bis(NHC) precursors have been synthesised by treatment of the corresponding [Au(NHC)Cl] derivatives with imidazol(idin)ium salts in the presence of K₂CO₃. The reactivity of the Au^I complexes towards PhICl₂ has revealed an influence of the nature of the NHC ligands present in the complex on the outcome of the oxidation reaction: small and more strongly electron-donating NHC ligands favoured the formation of a Au^IIIspecies. On the basis of these results, a Au^I complex bearing two 1-butyl-3-methylimidazol-2-ylidene (BMIM) ligands has been synthesised. This complex reacted with PhICl₂ and also – for the first time in Au-NHC systems – with PhI(OAc)₂ and PhI(OAc^F)₂ (OAc^F = trifluoroacetate), affording stable Au^III-(NHC)₂ complexes bearing acetate ligands.

Original language	English
Pages (from-to)	4111-4122
Number of pages	12
Journal	European Journal of Inorganic Chemistry
Volume	2016
Issue number	25
Early online date	11 Aug 2016
DOIs	https://doi.org/10.1002/ejic.201600791
Publication status	Published - 4 Sept 2016

Keywords

Gold
Carbene ligands
Nitrogen heterocycles
Oxidation
Hypervalent iodine

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© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1002/ejic.201600791
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title = "Synthesis of AuI- and AuIII-bis(NHC) complexes: ligand influence on oxidative addition to AuI species",

abstract = "The oxidation chemistry of a range of AuI-bis(NHC) (NHC = N-heterocyclic carbene) complexes with hypervalent iodine(III) oxidants has been explored. AuI-bis(NHC) precursors have been synthesised by treatment of the corresponding [Au(NHC)Cl] derivatives with imidazol(idin)ium salts in the presence of K2CO3. The reactivity of the AuI complexes towards PhICl2 has revealed an influence of the nature of the NHC ligands present in the complex on the outcome of the oxidation reaction: small and more strongly electron-donating NHC ligands favoured the formation of a AuIII species. On the basis of these results, a AuI complex bearing two 1-butyl-3-methylimidazol-2-ylidene (BMIM) ligands has been synthesised. This complex reacted with PhICl2 and also – for the first time in Au-NHC systems – with PhI(OAc)2 and PhI(OAcF)2 (OAcF = trifluoroacetate), affording stable AuIII-(NHC)2 complexes bearing acetate ligands.",

keywords = "Gold, Carbene ligands, Nitrogen heterocycles, Oxidation, Hypervalent iodine",

author = "Alba Collado-Martinez and Jan Bohnenberger and Mar{\'i}a-Jos{\'e} Oliva-Madrid and Pierrick Nun and Cordes, {David B.} and Slawin, {Alexandra M. Z.} and Nolan, {Steven P.}",

note = "The European Research Council (ERC), Advanced Investigator Award-FUNCAT and Syngenta are gratefully acknowledged for financial support.",

year = "2016",

month = sep,

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doi = "10.1002/ejic.201600791",

language = "English",

volume = "2016",

pages = "4111--4122",

journal = "European Journal of Inorganic Chemistry",

issn = "1099-0682",

publisher = "Wiley-Blackwell",

number = "25",

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TY - JOUR

T1 - Synthesis of AuI- and AuIII-bis(NHC) complexes: ligand influence on oxidative addition to AuI species

AU - Collado-Martinez, Alba

AU - Bohnenberger, Jan

AU - Oliva-Madrid, María-José

AU - Nun, Pierrick

AU - Cordes, David B.

AU - Slawin, Alexandra M. Z.

AU - Nolan, Steven P.

N1 - The European Research Council (ERC), Advanced Investigator Award-FUNCAT and Syngenta are gratefully acknowledged for financial support.

PY - 2016/9/4

Y1 - 2016/9/4

N2 - The oxidation chemistry of a range of AuI-bis(NHC) (NHC = N-heterocyclic carbene) complexes with hypervalent iodine(III) oxidants has been explored. AuI-bis(NHC) precursors have been synthesised by treatment of the corresponding [Au(NHC)Cl] derivatives with imidazol(idin)ium salts in the presence of K2CO3. The reactivity of the AuI complexes towards PhICl2 has revealed an influence of the nature of the NHC ligands present in the complex on the outcome of the oxidation reaction: small and more strongly electron-donating NHC ligands favoured the formation of a AuIII species. On the basis of these results, a AuI complex bearing two 1-butyl-3-methylimidazol-2-ylidene (BMIM) ligands has been synthesised. This complex reacted with PhICl2 and also – for the first time in Au-NHC systems – with PhI(OAc)2 and PhI(OAcF)2 (OAcF = trifluoroacetate), affording stable AuIII-(NHC)2 complexes bearing acetate ligands.

AB - The oxidation chemistry of a range of AuI-bis(NHC) (NHC = N-heterocyclic carbene) complexes with hypervalent iodine(III) oxidants has been explored. AuI-bis(NHC) precursors have been synthesised by treatment of the corresponding [Au(NHC)Cl] derivatives with imidazol(idin)ium salts in the presence of K2CO3. The reactivity of the AuI complexes towards PhICl2 has revealed an influence of the nature of the NHC ligands present in the complex on the outcome of the oxidation reaction: small and more strongly electron-donating NHC ligands favoured the formation of a AuIII species. On the basis of these results, a AuI complex bearing two 1-butyl-3-methylimidazol-2-ylidene (BMIM) ligands has been synthesised. This complex reacted with PhICl2 and also – for the first time in Au-NHC systems – with PhI(OAc)2 and PhI(OAcF)2 (OAcF = trifluoroacetate), affording stable AuIII-(NHC)2 complexes bearing acetate ligands.

KW - Gold

KW - Carbene ligands

KW - Nitrogen heterocycles

KW - Oxidation

KW - Hypervalent iodine

UR - http://onlinelibrary.wiley.com/wol1/doi/10.1002/ejic.201600791/suppinfo

U2 - 10.1002/ejic.201600791

DO - 10.1002/ejic.201600791

M3 - Article

SN - 1099-0682

VL - 2016

SP - 4111

EP - 4122

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 25

ER -

Synthesis of Au^I- and Au^III-bis(NHC) complexes: ligand influence on oxidative addition to Au^Ispecies

Abstract

Keywords

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FUNCAT: EU FP7 ERC Advanced Grant - FUNCAT - Fundamental Studies in Organometallic Chemistry and Homogeneous Catalysis