UNSPECIFIED (1993) CHARGE-TRANSFER INTERACTIONS BETWEEN BIPYRIDINIUM IONS AND OCTACYANO-MOLYBDATES AND OCTACYANO-TUNGSTATES. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS (6). pp. 885-889. ISSN 0300-9246

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Abstract

Investigation of the interaction between the 4,4'-bipyridinium(2+) cation (4,4'-H-2bipy2+) and the octacyanometalates(IV) [M(CN)8]4- (Mo or W) led to the isolation of [4,4'-H2bipy]2[W(CN8)].4.5H2O and its isomorphous molybdenum analogue. The spectroscopic properties of both and the X-ray structural characterization of the former [monoclinic, space group P2(1)/c, a = 11.281 (5), b = 9.198(5), c = 30.113(24) angstrom, beta = 91.21(5)degrees, Z = 4] are described. The [W(CN)8]4- anion has an approximate square-antiprismatic D4d configuration with average dimensions W-C 2.168, C-N 1.136 angstrom, W-C-N 177.0-degrees. The structure consists of a three-dimensional hydrogen-bonded framework and cation-anion interaction occurs mainly through the water molecules. The intensely coloured solids (hydrated and anhydrous) and aqueous solutions are discussed in terms of the ion pairs which exhibit an outer-sphere electron transfer between adjacent redox sites. The correlation between the structures of the hydrated solids, the close contact ion pairs of the anhydrous salt and the solvent-separated ion pairs (solution) are discussed.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
Publisher:	ROYAL SOC CHEMISTRY
ISSN:	0300-9246
Date:	21 March 1993
Number:	6
Number of Pages:	5
Page Range:	pp. 885-889
Publication Status:	Published
URI:	http://wrap.warwick.ac.uk/id/eprint/21453

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