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Structural systematics of some trinuclear alkynyl and diynyl Group 11 complexes containing dppm [dppm = CH₂(PPh₂)₂]

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dc.contributor.authorBruce, M.
dc.contributor.authorHalet, J.-F.
dc.contributor.authorLe Guennic, B.
dc.contributor.authorSkelton, B.
dc.contributor.authorSobolev, A.
dc.contributor.authorSumby, C.
dc.contributor.authorWhite, A.
dc.date.issued2018
dc.descriptionAvailable online 9 October 2017
dc.description.abstractIn this review the molecular structures of a series of trinuclear alkynyl and diynyl Group 11 cations [{M<inf>3</inf>(μ-dppm)<inf>3</inf>}(X)<inf>n</inf>]<sup>(3−</sup> <sup>n</sup> <sup>)+</sup> (M = Cu, Ag; n = 1, 2; where X is an alkynyl or diynyl group, an inorganic anion or solvent) are considered from the points of view of (i) the dimensions and geometries of the M<inf>3</inf>(P–P)<inf>3</inf> cores, (ii) the conformations of the dppm ligands, and (iii) the attachment of the alkynyl and diynyl ligands. In the crowded [M<inf>3</inf>(μ-dppm)<inf>3</inf>]<sup>3+</sup> core, the dppm ligands are arranged so that there is always one CH<inf>2</inf> group up and two down, to give pseudo mirror symmetry perpendicular to the M<inf>3</inf> plane (crystallographic in some cases). Attachment of the alkynyl or diynyl substituent(s) occurs roughly normal to the M<inf>3</inf> plane; according to their perpendicularity, the C(1) atom may be μ<inf>2</inf> or μ<inf>3</inf>. In most cases where only one alkynyl or diynyl ligand is present, a second ligand is also attached to the M<inf>3</inf> core. Unusual and interesting dispositions/conformations of the dppm ligands are widespread, among the mono–diynyl complexes in particular, whereby some phosphorus donor atoms lie at unusual distances out of the M<inf>3</inf> planes, a concomitant of strong agostic interactions between phenyl H atoms and the atoms of the open M<inf>3</inf> face, and weak M⋯M interactions. With one X group, C–H⋯M interactions persist on the other face, with C–H⋯X interactions with the alkyne affecting the inclination of the alkyne and the conformation of the Ph rings. With two substituents (one of which may be a loosely bound anion), similar interactions may occur, accompanied by twisting of the dppm chelate ring to displace P atoms from the M<inf>3</inf> plane. These factors possibly inhibit formation of the bis(diyndiyl) complexes, which are only obtained under more strongly basic conditions.
dc.description.statementofresponsibilityMichael I. Bruce, Jean-François Halet, Boris Le Guennic, Brian W. Skelton, Alexandre N. Sobolev, Christopher J. Sumby, Allan H. White
dc.identifier.citationCoordination Chemistry Reviews, 2018; 375:2-12
dc.identifier.doi10.1016/j.ccr.2017.09.021
dc.identifier.issn0010-8545
dc.identifier.issn1873-3840
dc.identifier.orcidBruce, M. [0000-0002-8377-7186]
dc.identifier.orcidSumby, C. [0000-0002-9713-9599]
dc.identifier.urihttp://hdl.handle.net/2440/114980
dc.language.isoen
dc.publisherElsevier BV
dc.relation.grantARC
dc.rights© 2017 Elsevier B.V. All rights reserved.
dc.source.urihttps://doi.org/10.1016/j.ccr.2017.09.021
dc.titleStructural systematics of some trinuclear alkynyl and diynyl Group 11 complexes containing dppm [dppm = CH₂(PPh₂)₂]
dc.title.alternativeStructural systematics of some trinuclear alkynyl and diynyl Group 11 complexes containing dppm [dppm = CH(2)(PPh(2))(2)]
dc.typeJournal article
pubs.publication-statusPublished

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