By AG Sykes

Advances in Inorganic Chemistry provides well timed and informative summaries of the present growth in numerous topic components inside inorganic chemistry, starting from bioinorganic to sturdy nation. This acclaimed serial good points studies written via specialists within the quarter and is an integral connection with complicated researchers. every one quantity of Advances in Inorganic Chemistry comprises an index, and every bankruptcy is totally referenced.

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Extra info for Advances in Inorganic Chemistry, Vol. 52

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The common structure for this family of cages consists of a {Mn404} heterocubane surrounded by an octanuclear manganese wheel, bridged by carboxylates and oxide ligands. The central heterocubane contains exclusively Mn(IV) sites, while the octanuclear wheel contains eight Mn(III) sites. Where the cages are redox-active, the reduction sites are the external Mn(III) centers (117), which means that the mono- and dinegative cages contain three oxidation states--Mn(II), Mn(III), and Mn(IV). , the octanuclear vanadium and chromium wheels (2 and 19) resemble the wheel in these {Mnl2} cages.

The dianionic members of the family reported, [Mn12012(O2CCR)16(H20)4] 2- [ R = CHC12, C6F5, C6H3(NO2)2], require electron-withdrawing carboxylate groups to stabilize the lower oxidation states. 27 cm -1. Therefore, comparing the three oxidation states, the ground state spins are {Mn12}, S = 10; {Mn12}-, S = y19. , {Mnl2} 2-, S -- 10. 5 cm -1 for the neutral species to about - 0 . 3 cm -1 for the dianion; this m a y reflect the replacement of Mn(III) centers by Mn(II) centers in the reduced compounds.

The cage was made by reaction of the oxocentered iron benzoate triangle with neopentanol in toluene. At the center of the cage six Fe(III) centers are arranged in a bitetrahedron, with a ~4-oxide at the center of each tetrahedron. The two centers in each tetrahedron that are not in the shared edge are bridged by further oxides, which also bridge to the final iron centers in the polyhedron; these are therefore tL3-oxides. The carboxylates bridged in a typical 1,3fashion, while the alkoxides are either t~2-bridging or terminal.

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