Manganese compounds dinuclear complexes

A dinuclear Mn111 porphyrin complex linked by an o-phenylene bridge (LI4) (Figure 32) [161] seems to be the first reported structurally well-defined manganese compound to oxidize H20 by a four-electron process. 

The reaction of [Fe(CN)6]3 and Schiff base manganese complexes give a polynuclear compound with [Fe—C=N—Mn] units.4 A dinuclear [Fe2(CN)i0]4- species is also known and has been studied extensively.49... 

Reviews have appeared of the photophysics of molybdenum complexes, primary and secondary processes in organometallic chemistry, flash photolysis of Pe(CO)5 and Cr(CO)g, dinuclear manganese carbonyl compounds, the photochemistry of metal complexes isolated in low temperature matrices, cluster complexes, diene complexes, photoproduction of coordinativeiy unsaturated species containing rhodium or iridium, and redox chemiluminescence of organometallic compounds.Synthetic and metal organic photochemistry in industry has also been reviewed. 

K[Re2(C0)g02H] is a dinuclear compound with 0x0 and hydroxo bridges. [M(C0)6]" compounds, where M = Tc or Re, are obtained similarly to the corresponding manganese complex. The salts of these Tc or Re cations are more stable than those of [Mn(CO)6]. [ (CO) ] compound, in contrast to the manganese complex, does not react with water. 

Sakiyama explored various dinuclear manganese complexes as catalase mimics derived from 2,6-bis N-[(2-dimethylamino)ethyl]iminomethyl-4-methylphenolate (2, Figure 10.1) and related ligands. Employing UV- ds and MS techniques both mono-and di-Mn -oxo intermediates could be detected [30]. Notably, the proposed mechanism (Scheme 10.2) is different from that reported for the manganese catalases and model compounds containing ligand 1 [30]. 

---