Structural systematics of some trinuclear alkynyl and diynyl Group 11 complexes containing dppm [dppm = CH₂(PPh₂)₂]
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(Accepted version)
Date
2018
Authors
Bruce, M.
Halet, J.-F.
Le Guennic, B.
Skelton, B.
Sobolev, A.
Sumby, C.
White, A.
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Journal article
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Coordination Chemistry Reviews, 2018; 375:2-12
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Michael I. Bruce, Jean-François Halet, Boris Le Guennic, Brian W. Skelton, Alexandre N. Sobolev, Christopher J. Sumby, Allan H. White
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Abstract
In 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.
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Available online 9 October 2017
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© 2017 Elsevier B.V. All rights reserved.