Ainscough, Eric W., Bowmaker, Graham A., Brodie, Andrew M., Freeman, Graham H., Hanna, John V., Jameson, Geoffrey B. and Otter, Carl A. (2011) Structural and spectroscopic characterization of silver(I) tribenzylphosphane complexes including chloro and bromo derivatives with unusual stoichiometries and an iodo complex with a Ag13I13 cluster core. Polyhedron, Vol.30 (No.4). pp. 638-646. doi:10.1016/j.poly.2010.11.031 ISSN 0277-5387.

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Abstract

The reaction of tribenzylphosphane (PBn3) with silver(I) halides, AgX (X = Cl, Br and I), afforded the cluster compound, [Ag13I13(PBn3)6 ] (1), a low-yielding ionic salt, [Ag(PBn3)2]8[AgCl3]Cl6·6H2O (2), and a non-stoichiometric compound, Ag∼11.5Br∼11.5(PBn3)16·∼5.5H2O (3). As well, reactions with the appropriate Ag salt and PBn3 in a 1:2 M ratio yielded [Ag(PBn3)2]PF6 (4), [Ag(PBn3)2]BF4 (5) and [Ag(PBn3)2Cl]·0.33CHCl3 (6) while [Ag(PBn3)2I] (7) was obtained when the ratio was 4:1. The iodo-cluster 1 has an onion-like structure with an iodide ion at its center surrounded trigonal-prismatically by an inner core of six silver ions. These silver ions are tetrahedrally coordinated to the innermost iodide ion and by six iodides that bridge to an outer layer of six silver ions which themselves are tetrahedrally coordinated by six bridging iodides and capped by the six PBn3 ligands. The top of the onion features a silver ion with three iodo ligands arranged in a near-planar trigonal arrangement around it. Single crystal X-ray crystallography shows the complexes 2 and 3 to contain columns of discrete [Ag(PBn3)2]+ cations with a linear P–Ag–P coordination, as also observed in the simple salts, 4 and 5, where the anion is [PF6]− and [BF4]−. The phenyl groups of PBn3 swing back over the silver to generate a sixfold phenyl embrace. However, in 3, although the PBn3 sites are fully occupied, about a quarter of the sixfold phenyl embraces are devoid of the object of their attention, the encapsulated silver ion. For 2, the [AgCl3]2− anions are trigonal-planar, three-coordinated. For 3, the appear as motifs in an approximately 25% silver-deficient Ag4 cluster. The crystal structures of the three-coordinate halides, 6 and 7, show that the geometry around the silver is close to a T-shape, with the chloride and iodide ions bound. The far-IR and 31P CP MAS NMR spectra of a selection of the new complexes confirm aspects of their symmetry as deduced from the crystallographic studies.

Item Type:	Journal Article
Subjects:	Q Science > QC Physics Q Science > QD Chemistry
Divisions:	Faculty of Science, Engineering and Medicine > Science > Physics
Library of Congress Subject Headings (LCSH):	X-rays -- Diffraction, Silver compounds, Spectrum analysis, Complex compounds -- Spectra
Journal or Publication Title:	Polyhedron
Publisher:	Pergamon
ISSN:	0277-5387
Official Date:	11 March 2011
Dates:	Date Event 11 March 2011 Published
Volume:	Vol.30
Number:	No.4
Page Range:	pp. 638-646
DOI:	10.1016/j.poly.2010.11.031
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
Funder:	Massey University , Engineering and Physical Sciences Research Council (EPSRC), University of Warwick , European Regional Development Fund (ERDF), Advantage West Midlands (AWM)

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