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• W2002468278 endingPage "1987" @default.
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• W2002468278 abstract "Six novel cyanide-bridged mixed-valence complexes. [(η5-C5H5)(PPh3)2M′(µ-CN)M(NH3)5][CF3SO3]3(M = Ru, M′= Ru or Os; M = Os, M′= Ru or Os) and [(η5-C5R5)(PPh3)2Ru(η-CN)Ru(NH3)5][CF3SO3]3(C5R5= C5H4Me or C5Me5), have been synthesised using a simple coupling reaction and characterised by electronic and infrared absorption spectroscopy and by cyclic voltammetry. They exhibit moderately intense (εmax≈ 2000–4000 dm3 mol–1 cm–1), broad (Δν½≈ 5000 cm–1) intervalence charge-transfer transitions in the visible spectrum, analysis of which reveals Robin–Day Class II behaviour (α2≈ 0.8–2.0%, Hrp≈ 1700–2000 cm–1). Outer-sphere effects upon the cyanide-bridge stretching frequency and all the intervalence charge-transfer band characteristics are reported and interpreted using linear correlations with respect to Gutmann solvent donicity, where appropriate, and simple perturbation arguments. The weak solvent dependence of the coupling element, Hrp, indicates that the charge-transfer mechanism proceeds primarily through an electron, rather than hole, transfer pathway. The intervalence charge-transfer bands of the cyclopentadienylosmium complexes exhibit a pronounced spin-orbit splitting, the relative intensities of the components also showing solvent dependence." @default.
• W2002468278 created "2016-06-24" @default.
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• W2002468278 date "1994-01-01" @default.
• W2002468278 modified "2023-09-23" @default.
• W2002468278 title "Synthesis and characterisation of cyanide-bridged heterobinuclear mixed-valence compounds based on cyclopentadienylorganophosphine-ruthenium(II) and -osmium(II) cyano and pentaammine-ruthenium(III) and -osmium(III) moieties" @default.
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• W2002468278 doi "https://doi.org/10.1039/dt9940001987" @default.
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