Manganese complexes periodates

Sulfones. The use of periodic acid to oxidize sulfides (16 examples, 84-99%) is efficiently catalyzed by a binuclear manganese complex. 

Practically all metal ions of the periodic system have been introduced into the electron-rich center of the porphyrin macrocycle, and a large variety of strange reactions has been discovered. We give examples of ruthenium, rhodium, and manganese complexes. 

Cationic arene tricarbonyl manganese complexes, usually isolated as their BF4-or PFg- salts, are yellow solids. They are stable to air in the solid state and can be stored for long periods provided that they are kept out of light. They are best purified by crystallization by slow diffusion of diethylether into acetone- or CH2Cl2-solutions of the complex. Only direct methods of complexation are reported here. For other methods, involving transformations of the arene in the complex, the reader is referred to Chap. 6, to reviews [68], and to the recent literature [69,70]. 

Ground-state electronic configuration is ls 2s 2p 3s 3p 3i 4s. Manganese compounds are known to exist in oxidation states ranging from —3 to +7 (Table 2). Both the lower and higher oxidation states are stabilized by complex formation. In its lower valence, manganese resembles its first row neighbors chromium and especially iron ia the Periodic Table. Commercially the most important valances are Mn, Mn ", or Mn ". ... 

With these highly oriented porphyrins regioselective oxidations were performed using the iron(III)- and manganese (Ill)-complexes 183 and 184, respectively, in the presence of sodium periodate, PhIO or 02/ascorbate. 

An unusual reaction, with loss of a phenyl group from HSnPh3, occurs with some din-uclear manganese-hydride carbonyl complexes (equation 84)240. The chemistry outlined in the previous equations, involving elimination of H2, occurs in many regions of the periodic table and produces good yields of the metal-tin bonded complex. 

The unique versatility of ruthenium as an oxidation catalyst continues to provide a stimulus for research on a variety of oxidative transformations. Its juxtaposition in the periodic table and close similarity to the biological redox elements, iron and manganese, coupled with the accessibility of various high-valent oxo species by reaction of lower-valent complexes with dioxygen make ruthenium an ideal candidate for suprabiotic catalysis. 

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