Heme and nonheme monoxygenases and dioxygenases catalyze important oxygen atom transfer reactions to substrates in the body. It is now well established that the cytochrome P450 enzymes react through the formation of a high-valent iron(IV)-oxo heme cation radical. Its precursor in the catalytic cycle, the iron(III)-hydroperoxo complex, was tested for catalytic activity and found to be a sluggish...

Current interests in the chemistry of high-nuclearity transition-metal complexes draw from their utility in the emerging science of nanomaterials, as models for the multimetal active sites of metal-storage proteins, and as single molecule magnets (SMMs). In addition, such super-sized molecules often show a variety of supramolecular interactions. The “self-assembly” process of generating a high-...

The reaction of Mn(OAc)2 x 4H2O with 2,6-dimethoxybenzoylsalicylhydrazide (H3dmbshz) leads to a dodecanuclear manganese metallamacrocycle [Mn12(dmbshz)12(EtOH)6], 1. The successive manganese centers are connected by the hydrazide N-N groups of the ligands in an alternating pentadentate binding mode, hexadentate binding mode. The alternation results in two alternating chelation modes around the ...

Density functional theory is used to explore possible mechanisms that lead to water oxidation by a bimetallic manganese catalyst developed by McKenzie and co-workers. On the basis of our calculations we propose that the key active intermediate is a mixed valent Mn(III)(μ-O)Mn(IV)-O˙ oxyl radical species, the oxyl centre being the site of nucleophilic attack by water. The mixed-valent species is...

The mercury (II) complex, Hg (Meca2en)I2 (1), containing bidentate Schiff base ligand  Meca2en = N,N′-bis[(E)-2-benzylidenepropylidene]ethane-1,2-diamine, has been synthesized and characterized by elemental analyses (CHN) and 1H-NMR spectroscopy. The crystal structure of 1 was determined using single-crystal X-ray diffraction. Structural investigation shows that 1 crystallizes in a monoclinic s...

We report the synthesis, crystal structure and Hirshfeld surface analysis of Fe(II) complex based on a pentadentate N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-(bis-2-pyridylmethyl)amine) polynitrile tcnspr (1,1,3,3-tetracyano-2-thiopropylpropenide) ligands, [Fe(N4Py)(tcnspr)](tcnspr) 1. The X-ray result, indicates that 1 is low-spin complex. coordinated molecule in cation exhibits disorder over tw...

The reactions of the Mn(III)(3) and Mn(II)Mn(III)(2) complexes [Mn(3)O(O(2)CEt)(6)(py)(3)][ClO(4)] and [Mn(3)O(O(2)CEt)(6)(py)(3)] with pyridine-2,6-dimethanol (pdmH(2)) afford the mixed-valence Mn(II)(6)Mn(III)(2) octanuclear complex [Mn(8)O(2)(py)(4)(O(2)CEt)(8)(L)(2)][ClO(4)](2) (1) and the Mn(II)(7)Mn(III)(2) enneanuclear complex [Mn(9)(O(2)CEt)(12)(pdm)(pdmH)(2)(L)(2)] (2), respectively. B...