Pseudo-base formation in the attempted synthesis of a conjugatively coupled bis(nitrosylruthenium) complex and spectroelectrochemistry of bipyrimidine-bridged dinuclear Ru(terpy)X precursor compounds (X = Cl, NO2)
, , , , und .
Dalton Transactions (2008)

Reaction of (μ-bpym)RuCl(terpy)2(PF6)2, bpym = 2,2'-bipyrimidine and terpy = 2,2':6',2''-terpyridine, with NaNO2 yields (μ-bpym)Ru(NO2)(terpy)2(PF6)2. In CH3CN/0.1 M Bu4NPF6 both dinuclear complexes can undergo two reversible bpym-centered 1-electron redn. processes and two metal-centered 1-electron oxidn. steps, the latter involving mixed-valent intermediates with weak intermetallic coupling. Acidification of (μ-bpym)Ru(NO2)(terpy)2(PF6)2 does not lead to the expected (μ-bpym)Ru(NO)(terpy)26+ but, probably because of the high charge, to the insol. but structurally and IR-spectroscopically characterized pseudo-base product syn-(μ-bpym-(4-OH))Ru(NO)(terpy)2(PF6)5. The addn. of one hydroxide to one of the 4-positions of bis-chelating bpym interrupts the arom. p conjugation and is accompanied by corresponding intra-pyrimidine bond length variations, however, the effect on the electronic interaction of the two different syn positioned RuNO6 moieties remains small, possibly due to their situation within the central mol. p plane. on SciFinder(R)
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