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|Title:||Non-innocent behaviour of ancillary and bridging ligands in homovalent and mixed-valent ruthenium complexes [A(2)Ru(mu-L)RuA(2)](n), A=2,4-pentanedionato or 2-phenylazopyridine, L2-=2,5-bis(2-oxidophenyl)pyrazine|
|Keywords:||Nuclear Magnetic Resonance|
|Publisher:||ROYAL SOC CHEMISTRY|
|Citation:||DALTON TRANSACTIONS, (23), 2411-2418|
|Abstract:||Structurally characterised 2,5-bis(2-hydroxyphenyl)pyrazine (H2L) can be partially or fully deprotonated to form the complexes [(acac)(2)Ru(mu-L)Ru(acac)(2)], , acac(-) = acetylacetonato 2,4-pentanedionato, [(pap)(2)Ru(mu-L)Ru(pap)(2)](ClO4)(2), (ClO4)(2), pap = 2-phenylazopyridine, or [(pap)(2)Ru(HL)](ClO4), (ClO4). Several reversible oxidation and reduction processes were observed in each case and were analysed with respect to oxidation state alternatives through EPR and UV-VIS-NIR spectroelectrochemistry. In relation to previously reported compounds with 2,2'-bipyridine as ancillary ligands the complex redox system (n) is distinguished by a preference for metal-based electron transfer whereas the systems (n) and (n) favour an invariant Ru-II state. Accordingly, the paramagnetic forms of (n), n = -, 0, +, exhibit metal-centred spin whereas the odd-electron intermediates (+), (3+) and  show radical-type EPR spectra. A comparison with analogous complexes involving the 3,6-bis(2-oxidophenyl)-1,2,4,5-tetrazine reveals the diminished pi acceptor capability of the pyrazine-containing bridge.|
|Appears in Collections:||Article|
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