-Oxoruthenium complexes supported by chiral tetradentate amine (N) ligands for hydrocarbon oxidations.

We report the first examples of ruthenium complexes -[(N)RuCl] and -[(N)Ru(OH)] supported by chiral tetradentate amine ligands (N), together with a high-valent -dioxo complex -[(N)Ru(O)] supported by the chiral N ligand mcp (mcp = ,'-dimethyl-,'-bis(pyridin-2-ylmethyl)cyclohexane-1,2-diamine). The X-ray crystal structures of -[(mcp)RuCl](ClO) (), -[(Memcp)RuCl]ClO () and -[(pdp)RuCl](ClO) () (Memcp = ,'-dimethyl-,'-bis((6-methylpyridin-2-yl)methyl)cyclohexane-1,2-diamine, pdp = 1,1'-bis(pyridin-2-ylmethyl)-2,2'-bipyrrolidine)) show that the ligands coordinate to the ruthenium centre in a -α configuration. In aqueous solutions, proton-coupled electron-transfer redox couples were observed for -[(mcp)Ru(OCCF)]ClO () and -[(pdp)Ru(OSCF)]CFSO ().

Water oxidation catalysed by iron complex of ,'-dimethyl-2,11-diaza[3,3](2,6)pyridinophane. Spectroscopy of iron-oxo intermediates and density functional theory calculations.

The macrocyclic [Fe(L1)Cl] (, L1 = ,'-dimethyl-2,11-diaza[3,3](2,6)pyridinophane) complex is an active catalyst for the oxidation of water to oxygen using [NH][Ce(NO)] (CAN), NaIO, or Oxone as the oxidant. The mechanism of -catalysed water oxidation was examined by spectroscopic methods and by O-labelling experiments, revealing that Fe[double bond, length as m-dash]O and/or Fe[double bond, length as m-dash]O species are likely to be involved in the reaction. The redox behaviour of and these high-valent Fe[double bond, length as m-dash]O species of L1 has been examined by both cyclic voltammetry and density functional theory (DFT) calculations.

Nonheme iron mediated oxidation of light alkanes with oxone: characterization of reactive oxoiron(IV) ligand cation radical intermediates by spectroscopic studies and DFT calculations.

The oxidation of light alkanes that is catalyzed by heme and nonheme iron enzymes is widely proposed to involve highly reactive {Fe(V)=O} species or {Fe(IV)=O} ligand cation radicals. The identification of these high-valent iron species and the development of an iron-catalyzed oxidation of light alkanes under mild conditions are of vital importance. Herein, a combination of tridentate and bidentate ligands was used for the generation of highly reactive nonheme {Fe=O} species.

Practical manganese-catalysed highly enantioselective cis-dihydroxylation of electron-deficient alkenes and detection of a cis-dioxomanganese(V) intermediate by high resolution ESI-MS analysis.

A practical protocol has been developed for asymmetric cis-dihydroxylation of electron-deficient alkenes with Oxone catalysed by a manganese complex bearing a chiral tetradentate N(4)-donor ligand affording cis-diols in up to 95% yield with up to 96% ee. Analysis of the reaction mixture by high resolution ESI-MS revealed the formation of a cis-dioxomanganese(V) intermediate.

cis-Dihydroxylation of alkenes with oxone catalyzed by iron complexes of a macrocyclic tetraaza ligand and reaction mechanism by ESI-MS spectrometry and DFT calculations.

[Fe(III)(L-N(4)Me(2))Cl(2)](+) (1, L-N(4)Me(2) = N,N'-dimethyl-2,11-diaza[3.3](2,6)pyridinophane) is an active catalyst for cis-dihydroxylation of various types of alkenes with oxone at room temperature using limiting amounts of alkene substrates. In the presence of 0.