A series of caesium manganese hexacyanoferrates is prepared; Cs(I)(1.78)Mn(II)[Fe(II)(CN)6]0.78[Fe(III)(CN)6](0.22) (1), Cs(I)(1.57)Mn(II)[Fe(II)(CN)6]0.57[Fe(III)(CN)6](0.43) (2), Cs(I)(1.51)Mn(II)[Fe(II)(CN)6]0.51[Fe(III)(CN)6](0.49) (3), and Cs(I)(0.94)Mn(II)[Fe(II)(CN)6]0.21[Fe(III)(CN)6](0.70).0.8H2O (4). 1-3 show charge-transfer phase transitions between the high-temperature (HT) and low-...

and theoretical study of a Mn(III)-Cu(II) dimer containing a Jahn-Teller compressed Mn ion' Dalton Transactions, vol 42, no. 1, pp. 207-216. General rights Copyright for the publications made accessible via the Edinburgh Research Explorer is retained by the author(s) and / or other copyright owners and it is a condition of accessing these publications that users recognise and abide by the legal...

The potential for Mn oxides to modify the biogeochemical behavior of U during reduction by the subsurface bacterium Shewanella putrefaciens strain CN32 was investigated using synthetic Mn(III/IV) oxides (pyrolusite [ -MnO2], bixbyite [Mn2O3] and K -birnessite [K4Mn14O27 8H2O]). In the absence of bacteria, pyrolusite and bixbyite oxidized biogenic uraninite (UO2[s]) to soluble U(VI) species, wit...

The chiral triplesalen ligand H6chand(RR) has been used to synthesize the chiral heptanuclear complexes [{(chand(RR))Mn(III)3}2{Fe(II)(CN)6}](ClO4)2 ((RR)[Mn(III)6Fe(II)](ClO4)2) and [{(chand(RR))Fe(III)3}2{Fe(II)(CN)6}](ClO4)2 ((RR)[Fe(III)6Fe(II)](ClO4)2), which have been characterized by single-crystal X-ray diffraction, mass spectrometry, elemental analysis, FT-IR, Mössbauer, and UV-vis spe...

The activation parameters and the rate constants of the water-exchange reactions of Mn(III)TE-2-PyP(5+) (meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin) as cationic, Mn(III)TnHex-2-PyP(5+) (meso-tetrakis(N-n-hexylpyridinium-2-yl)porphyrin) as sterically shielded cationic, and Mn(III)TSPP(3-) (meso-tetrakis(4-sulfonatophenyl)porphyrin) as anionic manganese(iii) porphyrins were determined from th...

Reactive Mn(IV) oxide minerals are ubiquitous in the environment and control the bioavailability and distribution of many toxic and essential elements and organic compounds. Their formation is thought to be dependent on microbial enzymes, because spontaneous Mn(II) to Mn(IV) oxidation is slow. Several species of marine Bacillus spores oxidize Mn(II) on their exosporium, the outermost layer of t...

Ribonucleotide reductases (RNRs) utilize radical chemistry to reduce nucleotides to deoxynucleotides in all organisms. In the class Ia and Ib RNRs, this reaction requires a stable tyrosyl radical (Y(•)) generated by oxidation of a reduced dinuclear metal cluster. The Fe(III)2-Y(•) cofactor in the NrdB subunit of the class Ia RNRs can be generated by self-assembly from Fe(II)2-NrdB, O2, and a re...

Microbially mediated oxidation of Mn(II) to Mn(III/IV) oxides influences the cycling of metals and remineralization of carbon. Despite the prevalence of Mn(II)-bearing minerals in nature, little is known regarding the ability of microbes to oxidize mineral-hosted Mn(II). Here, we explored oxidation of the Mn(II)-bearing mineral rhodochrosite (MnCO3 ) and characteristics of ensuing Mn oxides by ...

A series of ferrocenyl-functionalized β-diketonato manganese(III) complexes, [Mn(FcCOCHCOR)₃] with R = CF₃, CH₃, Ph (phenyl) and Fc (ferrocenyl) was subjected to a systematic XPS study of the Mn 2p3/2 and Fe 2p3/2 core-level photoelectron lines and their satellite structures. A charge-transfer process from the β-diketonato ligand to the Mn(III) metal center is responsible for the prominent shak...