Electronic structure and catalytic aspects of [Ru(tpm)(bqdi)(Cl/H2O)]n, tpm = tris(1-pyrazolyl)methane and bqdi = o-benzoquinonediimine.

The diamagnetic complexes [Ru(tpm)(bqdi)(Cl)]ClO(4) ([1]ClO(4)) (tpm = tris(1-pyrazolyl)methane, bqdi = o-benzoquinonediimine) and [Ru(tpm)(bqdi)(H(2)O)](ClO(4))(2) ([2](ClO(4))(2)) have been synthesized. The valence state-sensitive bond distances of coordinated bqdi [C-N: 1.311(5)/1.322(5) Å in [1]ClO(4); 1.316(7)/1.314(7) Å in molecule A and 1.315(6)/1.299(7) Å in molecule B of [2](ClO(4))(2)] imply its fully oxidised quinonediimine (bqdi(0)) character. DFT calculations of 1(+) confirm the {Ru(II)-bqdi(0)} versus the antiferromagnetically coupled {Ru(III)-bqdi˙(-)} alternative. The (1)H NMR spectra of [1]ClO(4) in different solvents show variations in chemical shift positions of the NH (bqdi) and CH (tpm) proton resonances due to their different degrees of acidity in different solvents. In CH(3)CN/0.1 mol dm(-3) Et(4)NClO(4), [1]ClO(4) undergoes one reversible Ru(II)⇌ Ru(III) oxidation and two reductions, the reversible first electron uptake being bqdi based (bqdi(0)/bqdi˙(-)). The electrogenerated paramagnetic species {Ru(III)-bqdi(0)}(1(2+)) and {Ru(II)-Q˙(-)}(1) exhibit Ru(III)-type (1(2+): <g> = 2.211/Δg = 0.580) and radical-type (1: g = 1.988) EPR signals, respectively, as is confirmed by calculated spin densities (Ru: 0.767 in 1(2+), bqdi: 0.857 in 1). The aqua complex [2](ClO(4))(2) exhibits two one-electron oxidations at pH = 7, suggesting the formation of {Ru(IV)[double bond, length as m-dash]O} species. The electronic spectral features of 1(n) (n = charge associated with the different redox states of the chloro complex: 2+, 1+, 0) in CH(3)CN and of 2(2+) in H(2)O have been interpreted based on the TD-DFT calculations. The application potential of the aqua complex 2(2+) as a pre-catalyst towards the epoxidation of olefins has been explored in the presence of the sacrificial oxidant PhI(OAc)(2) in CH(2)Cl(2) at 298 K, showing the desired selectivity with a wide variety of alkenes. DFT calculations based on styrene as the model substrate predict that the epoxidation reaction proceeds through a concerted transition state pathway.