A mononuclear high-valent trans-dioxoruthenium(VI) complex, trans-[Ru(VI)(TMC)(O)2](2+) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was synthesized and characterized by various spectroscopic techniques and X-ray crystallography. The reactivity of the trans-[Ru(VI)(TMC)(O)2](2+) complex was investigated in hydride transfer and hydrogen atom transfer reactions. The mechanism of hydride transfer from dihydronicotinamide adenine dinucleotide (NADH) analogues to trans-[Ru(VI)(TMC)(O)2](2+), which proceeds via a proton-coupled electron transfer (PCET), followed by a rapid electron transfer (ET), has been proposed by the observation of a good linear correlation between the log rate constants of trans-[Ru(VI)(TMC)(O)2](2+) and p-chloranil (Cl4Q) and a large kinetic isotope effect (KIE) value of 13(1). In the case of the oxidation of alkyl hydrocarbons by the trans-[Ru(VI)(TMC)(O)2](2+) complex, the second-order rate constants were dependent on the C-H bond dissociation energy (BDE) of the substrates, and a large KIE value of 26(2) was obtained in the oxidation of xanthene and deuterated xanthene-d2 by the trans-[Ru(VI)(TMC)(O)2](2+) complex, indicating that the C-H bond activation of alkyl hydrocarbons proceeds via an H-atom abstraction in the rate-determining step.

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A new non-heme Mn(iii)–peroxo (1a) has been generated, characterized and reactivity is in aldehyde deformylation reaction. A nucleophilic reactivity of 1a in aldehyde oxidation is proposed.

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A nonheme single-metal-site Mn-complex i.e. [Mn(N3Py2)H2O] (ClO4)2; where N3Py2 = N,N′-dimethyl-N-(2-(methyl(pyridin-2-ylmethyl)amino)-ethyl-N′-(pyridin-2-ylmethyl)ethane-1,2-diamine) displays electrochemical water oxidation ability in a wide pH range.