Preparation of tetrabutylammonium salt of a mono-Ru(III)-substituted α-Keggin-type silicotungstate with a 4,4′-bipyridine ligand and its electrochemical behaviour in organic solvents

Ogo Shuhei

Moroi Sachie

Ueda Tadaharu

Komaguchi Kenji

Hayakawa Shinjirou

Ide Yusuke

Sano Tsuneji

Sadakane Masahiro

Dalton Transactions

The tetrabutylammonium (TBA) salt of a mono-ruthenium(III)-substituted α-Keggin-type silicotungstate with a 4,4′-bipyridine (bipy) ligand, TBA5[α-SiW11O39RuIII(bipy)] (1), which is soluble in various organic solvents, was prepared by a cation exchange reaction of Cs5[α-SiW11O39RuIII(bipy)] with tetrabutylammonium bromide. Compound 1 was characterised using IR, 1H-NMR, elemental analysis, single crystal X-ray analysis, X-ray absorption near-edge structure (XANES) analysis (Ru L3-edge), electron spin resonance (ESR), cyclic voltammetry (CV) and UV-Vis. Single crystal X-ray analysis of 1 revealed that the RuIII unit was incorporated into the α-Keggin-type silicotungstate framework and coordinated by a bipy molecule through a Ru–N bond. CV indicated that the incorporated RuIII-bipy was reversibly oxidised to the RuIV-bipy derivative and reduced to the RuII-bipy derivative in organic solvents. The redox potential of RuIV/III-bipy was found to be affected by organic solvents. Moreover, the RuV-bipy derivative was observed in acetonitrile.

Chemistry [ 430 ]

eng

Royal Society of Chemistry

Copyright (c) The Royal Society of Chemistry 2013

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[ISSN] 1477-9226

[NCID] AA11810256

[DOI] 10.1039/c3dt50300c

[PMID] 23532376