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Mono- and dimeric complexes of an asymmetric heterotopic P,CNHC,pyr ligand

Mono- and dimeric complexes of an asymmetric heterotopic P,CNHC,pyr ligand
Mono- and dimeric complexes of an asymmetric heterotopic P,CNHC,pyr ligand
An asymmetric heterotopic ligand (S-NMeCP) containing a central bicyclic, expanded-ring NHC with one pyridyl and one phosphine exo-substituent has been synthesised and its coordination chemistry with selected late transition metals investigated. The amidinium precursor [S-NMeCHP]PF6 shows variable coordination modes with Ag(I), Cu(I) and Au(I) depending on the L : M ratio. The reaction of two mols of [S-NMeCHP]PF6 with [Cu(MeCN)4]BF4, AgBF4 or Au(THT)Cl gives the bis-ligand complexes [Cu(?-P-NMeCHP)2(CH3CN)2]BF4·(PF6)2, 1, and [M(?-P-NMeCHP)2]X·(PF6)2 (3: M = Ag, X = BF4; 6: M = Au, X = Cl) respectively. The 1 : 1 reaction of [S-NMeCHP]PF6 with AgOTf gave the head-to-tail dimer H,T-[Ag2(?-N,P-NMeCHP)2(?-OTf)2](PF6)2, 2, whereas the analogous reaction with Au(THT)Cl gave monomeric [Au(?-P-NMeCHP)Cl]PF6, 5. Complex 2 was converted to H,T-[Ag2(?-C,P-NMeCP)2](PF6)2, 4, upon addition of base, while 6 gave [Au(?-C-NMeCP)2]Cl, 8, when treated likewise. Reaction of [S-NMeCHP]PF6 with Ni(1,5-COD)2 gave the oxidative addition/insertion product [Ni(?3-N,C,P-NMeCP)(?3-C8H13)]PF6, 9, which converted to [Ni(?3-N,C,P-NMeCP)Cl]PF6, 10, upon exposure of a CHCl3 solution to air. Complex 10 showed conformational isomerism that was also present in [Rh(?3-N,C,P-NMeCP)(CO)]PF6, 14, prepared from the precursor complex [Rh(?-P-NMeCHP)(acac)(CO)]PF6, 13, upon heating in C6H5Cl. [Pt(?3-N,C,P-NMeCP)(Cl)]PF6, 12, derived from trans-[Pt(?-P-NMeCHP)2(Cl)2](PF6)2, 11, was isolated as a single conformer.
0300-9246
13347-13360
Bouché, Mathilde
0af25a31-2ac3-49d2-8fec-e20f04adfa17
Mordan, Michael
672f89fe-d892-4dea-be03-b83c8649b53a
Kariuki, Benson M.
634ee7db-bcd1-4544-b667-2ad8c48ecedd
Coles, Simon
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Christensen, Jeppe
f37d3a1e-05d9-4144-8af2-bd29ead7d9c3
Newman, Paul D.
42e7ca00-b874-4cfb-a74a-6308015c4a8e
Bouché, Mathilde
0af25a31-2ac3-49d2-8fec-e20f04adfa17
Mordan, Michael
672f89fe-d892-4dea-be03-b83c8649b53a
Kariuki, Benson M.
634ee7db-bcd1-4544-b667-2ad8c48ecedd
Coles, Simon
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Christensen, Jeppe
f37d3a1e-05d9-4144-8af2-bd29ead7d9c3
Newman, Paul D.
42e7ca00-b874-4cfb-a74a-6308015c4a8e

Bouché, Mathilde, Mordan, Michael, Kariuki, Benson M., Coles, Simon, Christensen, Jeppe and Newman, Paul D. (2016) Mono- and dimeric complexes of an asymmetric heterotopic P,CNHC,pyr ligand. Dalton Transactions, 45 (34), 13347-13360. (doi:10.1039/c6dt02476a). (PMID:27461718)

Record type: Article

Abstract

An asymmetric heterotopic ligand (S-NMeCP) containing a central bicyclic, expanded-ring NHC with one pyridyl and one phosphine exo-substituent has been synthesised and its coordination chemistry with selected late transition metals investigated. The amidinium precursor [S-NMeCHP]PF6 shows variable coordination modes with Ag(I), Cu(I) and Au(I) depending on the L : M ratio. The reaction of two mols of [S-NMeCHP]PF6 with [Cu(MeCN)4]BF4, AgBF4 or Au(THT)Cl gives the bis-ligand complexes [Cu(?-P-NMeCHP)2(CH3CN)2]BF4·(PF6)2, 1, and [M(?-P-NMeCHP)2]X·(PF6)2 (3: M = Ag, X = BF4; 6: M = Au, X = Cl) respectively. The 1 : 1 reaction of [S-NMeCHP]PF6 with AgOTf gave the head-to-tail dimer H,T-[Ag2(?-N,P-NMeCHP)2(?-OTf)2](PF6)2, 2, whereas the analogous reaction with Au(THT)Cl gave monomeric [Au(?-P-NMeCHP)Cl]PF6, 5. Complex 2 was converted to H,T-[Ag2(?-C,P-NMeCP)2](PF6)2, 4, upon addition of base, while 6 gave [Au(?-C-NMeCP)2]Cl, 8, when treated likewise. Reaction of [S-NMeCHP]PF6 with Ni(1,5-COD)2 gave the oxidative addition/insertion product [Ni(?3-N,C,P-NMeCP)(?3-C8H13)]PF6, 9, which converted to [Ni(?3-N,C,P-NMeCP)Cl]PF6, 10, upon exposure of a CHCl3 solution to air. Complex 10 showed conformational isomerism that was also present in [Rh(?3-N,C,P-NMeCP)(CO)]PF6, 14, prepared from the precursor complex [Rh(?-P-NMeCHP)(acac)(CO)]PF6, 13, upon heating in C6H5Cl. [Pt(?3-N,C,P-NMeCP)(Cl)]PF6, 12, derived from trans-[Pt(?-P-NMeCHP)2(Cl)2](PF6)2, 11, was isolated as a single conformer.

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Accepted/In Press date: 14 July 2016
e-pub ahead of print date: 18 July 2016
Published date: 14 September 2016
Organisations: Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 403369
URI: https://eprints.soton.ac.uk/id/eprint/403369
ISSN: 0300-9246
PURE UUID: 00935c1b-4d9e-498c-823b-d4adfbefa73c
ORCID for Simon Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 30 Nov 2016 12:02
Last modified: 06 Jun 2018 12:54

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Contributors

Author: Mathilde Bouché
Author: Michael Mordan
Author: Benson M. Kariuki
Author: Simon Coles ORCID iD
Author: Jeppe Christensen
Author: Paul D. Newman

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