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Issue 39, 2007
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Transition metal vinylidene complexes as supramolecular building blocks: nucleobase-mediated self-assembly of crystals with hexagonal symmetry

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Abstract

Reaction of the ruthenium half sandwich compound RuCl(η5-C5H5)(PPh3)2 with the uracil (Ur) substituted alkyne HC[triple bond, length as m-dash]CUr in the presence of halide scavengers NH4X (X = PF6, BF4, OTf) results in the formation of the vinylidene complexes [Ru([double bond, length as m-dash]C[double bond, length as m-dash]CHUr)(η5-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(η7-C7H7)(dppe)([double bond, length as m-dash]C[double bond, length as m-dash]CHUr)][BF4] (dppe = 1,2-bis(diphenylphosphino)ethane) has also been prepared, but forms symmetric dimers in the solid state.

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

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Publication details

The article was received on 21 Jun 2007, accepted on 30 Jul 2007 and first published on 29 Aug 2007


Article type: Paper
DOI: 10.1039/B709483C
Citation: Dalton Trans., 2007,0, 4427-4438
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    Transition metal vinylidene complexes as supramolecular building blocks: nucleobase-mediated self-assembly of crystals with hexagonal symmetry

    M. J. Cowley, J. M. Lynam and A. C. Whitwood, Dalton Trans., 2007, 0, 4427
    DOI: 10.1039/B709483C

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