Mercury complexes of N-heterocyclic carbenes derived from imidazolium-linked cyclophanes: synthesis, structure, and reactivity

A range of mercury-imidazolylidene complexes have been prepared by reaction of imidazolium-linked cyclophanes with mercury(II) acetate. For cyclophanes based on meta-xylyl groups the mercury complexes are mononuclear and exhibit unprecedented structures in which the mercury atom is bound within the...

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Main Authors: Baker, M. V., Brown, David, Haque, R. A., Simpson, P. V., Skelton, B. W., White, A. H., Williams, C. C.
Format: Journal Article
Published: ACS Publications 2009
Online Access:http://pubs.acs.org/doi/abs/10.1021/om8011745
http://hdl.handle.net/20.500.11937/31716
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author Baker, M. V.
Brown, David
Haque, R. A.
Simpson, P. V.
Skelton, B. W.
White, A. H.
Williams, C. C.
author_facet Baker, M. V.
Brown, David
Haque, R. A.
Simpson, P. V.
Skelton, B. W.
White, A. H.
Williams, C. C.
author_sort Baker, M. V.
building Curtin Institutional Repository
collection Online Access
description A range of mercury-imidazolylidene complexes have been prepared by reaction of imidazolium-linked cyclophanes with mercury(II) acetate. For cyclophanes based on meta-xylyl groups the mercury complexes are mononuclear and exhibit unprecedented structures in which the mercury atom is bound within the cyclophane ring, the two NHC donors being mutually trans. For cyclophanes based on ortho-xylyl or 2,6-lutidinediyl groups the mercury complexes are dinuclearwith a [Hg(mu-L)2Hg] core, in which each mercury atom is coordinated by one NHC from each cyclophane unit. The mononuclear and dinuclear complexes have been structurally characterized. Studies of the NHC-pyridinophane mercury complex indicated that the NHC-Hg bonding is labile,suggesting that the dinuclear complex based on the [Hg(mu-L)2Hg] core existed in equilibrium with amononuclear complex [HgL]. The labile nature of the NHC-Hg bonding was further established by a redox transmetalation reaction of a dinuclear NHC-Hg(II) complex with a Pd(0) source, which afforded an NHC-Pd(II) complex.
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spelling curtin-20.500.11937-317162019-02-19T05:35:34Z Mercury complexes of N-heterocyclic carbenes derived from imidazolium-linked cyclophanes: synthesis, structure, and reactivity Baker, M. V. Brown, David Haque, R. A. Simpson, P. V. Skelton, B. W. White, A. H. Williams, C. C. A range of mercury-imidazolylidene complexes have been prepared by reaction of imidazolium-linked cyclophanes with mercury(II) acetate. For cyclophanes based on meta-xylyl groups the mercury complexes are mononuclear and exhibit unprecedented structures in which the mercury atom is bound within the cyclophane ring, the two NHC donors being mutually trans. For cyclophanes based on ortho-xylyl or 2,6-lutidinediyl groups the mercury complexes are dinuclearwith a [Hg(mu-L)2Hg] core, in which each mercury atom is coordinated by one NHC from each cyclophane unit. The mononuclear and dinuclear complexes have been structurally characterized. Studies of the NHC-pyridinophane mercury complex indicated that the NHC-Hg bonding is labile,suggesting that the dinuclear complex based on the [Hg(mu-L)2Hg] core existed in equilibrium with amononuclear complex [HgL]. The labile nature of the NHC-Hg bonding was further established by a redox transmetalation reaction of a dinuclear NHC-Hg(II) complex with a Pd(0) source, which afforded an NHC-Pd(II) complex. 2009 Journal Article http://hdl.handle.net/20.500.11937/31716 http://pubs.acs.org/doi/abs/10.1021/om8011745 ACS Publications restricted
spellingShingle Baker, M. V.
Brown, David
Haque, R. A.
Simpson, P. V.
Skelton, B. W.
White, A. H.
Williams, C. C.
Mercury complexes of N-heterocyclic carbenes derived from imidazolium-linked cyclophanes: synthesis, structure, and reactivity
title Mercury complexes of N-heterocyclic carbenes derived from imidazolium-linked cyclophanes: synthesis, structure, and reactivity
title_full Mercury complexes of N-heterocyclic carbenes derived from imidazolium-linked cyclophanes: synthesis, structure, and reactivity
title_fullStr Mercury complexes of N-heterocyclic carbenes derived from imidazolium-linked cyclophanes: synthesis, structure, and reactivity
title_full_unstemmed Mercury complexes of N-heterocyclic carbenes derived from imidazolium-linked cyclophanes: synthesis, structure, and reactivity
title_short Mercury complexes of N-heterocyclic carbenes derived from imidazolium-linked cyclophanes: synthesis, structure, and reactivity
title_sort mercury complexes of n-heterocyclic carbenes derived from imidazolium-linked cyclophanes: synthesis, structure, and reactivity
url http://pubs.acs.org/doi/abs/10.1021/om8011745
http://hdl.handle.net/20.500.11937/31716