A Mn(II) complex, [Mn(dpeo)2](2+) (dpeo=1,2-di(pyridin-2-yl)ethanone oxime), activates O2, with ensuing stepwise oxidation of the methylene group in the ligands providing an alkoxide and ultimately a ketone group. X-ray crystal-structure analysis of an intermediate homoleptic alkoxide Mn(III) complex shows tridentate binding of the ligand via the two pyridyl groups and the newly installed alkoxide moiety, with the oxime group no longer coordinated. The structure of a Mn(II) complex of the final ketone ligand, cis-[MnBr2(hidpe)2] (hidpe=2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone) shows that bidentate oxime/pyridine coordination has been resumed. H2(18)O and (18)O2 labeling experiments suggest that the inserted O atoms originate from two different O2 molecules. The progress of the oxygenation was monitored through changes in the resonance-enhanced Raman bands of the oxime unit.
Quadruple helical structures are assembled around a tetranuclear cubane structure using four chiral tridentate ligands and two ligands coordinating diagonally across a face. Stereoselectivity in the complex formation is observed.
Herein, we introduce the concept of pseudoisotope to describe particles which have similar chemistry but different masses. Examples include ligands with different substituents or metal ions with identical charges and similar coordination properties. Mixtures of pseudoisotopes may be used to establish rapidly the nuclearity of polynuclear species by electrospray ionization-mass spectrometry. Pseudoisotope exchange allows the study of the dynamics of polynuclear complexes, and shows these reactions may be surprisingly slow. The evolution of the mass spectra indicates the degree of fragmentation occurring during the exchange.
The coordination chemistry of tartronic acid, , with copper(ii) has been investigated. Structures of two complexes are reported containing respectively the complex [Cu(-2H)2Cl](3-) where acts as a bidentate ligand through carboxylates, and [Cu3(-3H)3](3-) where the alcohol function is deprotonated to bridge two coppers in a triangular trinuclear complex. The latter species undergoes facile oxidation leading to carbon-carbon bond formation. The magnetic and EPR properties of the trinuclear complex have been studied in detail.
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