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Transition metal vinylidene complexes as supramolecular building blocks: nucleobase-mediated self-assembly of crystals with hexagonal symmetry

Cowley, M.J., Lynam, J.M. and Whitwood, A.C. (2007) Transition metal vinylidene complexes as supramolecular building blocks: nucleobase-mediated self-assembly of crystals with hexagonal symmetry. Dalton Transactions, 39. pp. 4427-4438. ISSN 1477-9226

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Abstract

Reaction of the ruthenium half sandwich compound RuCl(5-C5H5)(PPh3)2 with the uracil (Ur) substituted alkyne HCCUr in the presence of halide scavengers NH4X (X = PF6, BF4, OTf) results in the formation of the vinylidene complexes [Ru(CCHUr)(5-C5H5)(PPh3)2][X] which crystallize in the hexagonal space group P6(3)/m. The hexagonal symmetry inherent to the system is due to the formation of a hydrogen bonded array mediated by the two sets of donor–acceptor units on the uracil, resulting in the formation of a cyclic rosette containing six ruthenium cations. In solution the 1H and 31P{1H} NMR spectra of the vinylidene complexes are both concentration and temperature dependent, in accord with the presence of monomer–dimer equilibria in which the rate of rotation of the vinylidene group is fast on the NMR timescale in the monomeric species, but slow in the dimers. The isoelectronic molybdenum-containing vinylidene complex [Mo(7-C7H7)(dppe)(CCHUr)][BF4] (dppe = 1,2-bis(diphenylphosphino)ethane) has also been prepared, but forms symmetric dimers in the solid state.

Item Type: Article
Institution: The University of York
Academic Units: The University of York > Chemistry (York)
Depositing User: York RAE Import
Date Deposited: 23 Jun 2009 13:19
Last Modified: 23 Jun 2009 13:19
Published Version: http://dx.doi.org/10.1039/b709483c
Status: Published
Publisher: Royal Society of Chemistry
Identification Number: 10.1039/b709483c
URI: http://eprints.whiterose.ac.uk/id/eprint/5952

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