Tetrakis(phenanthroline)di-.mu.-oxodimanganese(III,IV) tris(hexafluorophosphate).cntdot.acetonitrile and tetrakis(phenanthroline)di-.mu.-oxodimanganese(IV) tetraperchlorate.cntdot.acetonitrile: crystal structure analyses at 100 K, interpretation of disorder, and optical, magnetic, and electrochemical results

Abstract

Contribution from the Institut für Anorganische Chemie and the Laboratorium für Kristallographie, Universitat Bern, Bern, Switzerland [(phen)2MnIV(/t-0)2Mnni(phen)2](PF6)3*CH3CN and [(phen)2MnIV(M-0)2MnIV(phen)2](a04)4-CH3CN (phen = 1,10-Phenanthroline): Crystal Structure Analyses at 100 K, Interpretation of Disorder, and Optical, Magnetic, and Electrochemical Results

On the Reaction Mechanism of the Complete Intermolecular O2 Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

“…The structure and properties of a diversity of complexes with the general structure (LM) n -O 2 (n = 1, 2) have been described. [2,3,[6][7][8][9][10][11][12] LM-O 2 adducts present usually end-on or side-on coordination modes (see Scheme 1) and can react to give (LM) 2 -O 2 binuclear complexes, or LM-O 2 -L'M' when two different metal centers are involved, where the most frequent coordination modes are mh 2 :h 2 -O 2 in many Cu complexes, [2,11] bis(m-O) in Cu, [2,11] Mn, [13][14][15][16][17] Scheme 1. Metal-O 2 coordination modes.…”

High-Pressure Study of Oxo-bridged Mixed-Valent MnIII/MnIV Dimers High-Pressure Study of Oxo-bridged Mixed-Valent MnIII/MnIV Dimers

“…4 and 5) using the Hamiltonian of Eq. 1 suggest strong antiferromagnetic exchange in 1·3CH 3 CN (J = −177 cm −1 , g = 1.96) and in 2 (J = −185 cm −1 , g = 1.98) [44].…”

XANES, EXAFS and Kbeta spectroscopic studies of the oxygen-evolving complex in Photosystem II

“…Two similar complexes were crystallized by Stebler et al, 303 the Mn 2 (III,IV) complex with PF 6 counterions and the region is known to be extremely sensitive to the ligand geometry; 56 thus, it is not surprising that the changes in the pre-edge region in these complexes are dominated by the change in ligand environment of a mono-µ-oxo bridging compound to a di-µ-oxo bridging compound.…”

“…particularly dichroic, the EXAFS spectra taken at the same rotation angles φ and χ are much more dichroic. This is expected because the di-µ-oxo Mn-Mn moiety is planar; 303 thus, an orientation in which the X-ray E vector is parallel to the Mn-Mn vector will also maximize the contribution from the di-µ-oxo bridges. Conversely, an orientation in which the X -ray E vector is perpendicular to the Mn-Mn vector will minimize the contributions from both Mn-Mn backscattering and backscattering from the di-µ-oxo bridges, and the only remaining significant contributions will be from bridging ligands.…”