Manganese thiolate complexes

Various insertion reactions occur when metal thiolate complexes are treated with fluorinated alkynes under different reaction conditions. The manganese thiolate complexes of type 381 (R = Cp3, QFj) react with hexafluorobut-2-yne at 20°C in pentane to give an insertion product acting... 

Within this context, the present article concentrates on transition metal cluster complexes of cobalt, iron and manganese with mixed chalcogen/carbonyl ligand spheres obtained by reaction of simple binary metal carbonyls with alkali-metal sulfides, alkali-metal thiolates or transition-metal thiolate complexes and their selenium or tellurium counterparts. 

Structurally characterized trivalent manganese imidazole or imid-azolate complexes are also extremely rare. Current examples are limited to Mn(III) porphyrins (61), Mn(III) thiolates (Section III,B)> a Mn(III) salicylate complex (Section IV,B) and Mn(III) and Mn(IV) carboxylate complexes (Section VI,B) (62). None of these complexes contains a Mn-to-imidazole ratio greater than two consequently, no structural model for Mn SOD exists presently in Mn coordination chemistry. However, a five-coordinate Mn(II) monomer with three imidazole ligands, Mn(2-Me-ImH)3Cl2 (ImH = imidazole), has been characterized by X-ray diffraction techniques (63). 

Complexes of Manganese Carbonyl Having Bridging Thiolate Ligands 115... 

USE OF (BENZENETraOLATO)TRIBUTYLTIN TO PREPARE COMPLEXES OF MANGANESE CARBONYL HAVING BRIDGING THIOLATE LIGANDS... 

A large fraction of the binuclear mixed chalcogen/carbonyl transition metal complexes of iron and manganese contain the M2E (CO)6 core with the butterfly-type structure (n = 2) or substructure (n — 3, see Section 1.10.3). As an example of a complex with thiolate ligands, the structure of [Fe2(SC3H7)2(CO)6] is shown in... 

In contrast to iron and manganese, the number of trinuclear cobalt complexes is comparatively small. The reaction of [Co2(CO)s] with 2-propane thiolate or with C3H7SSC3H7 in methanol under solvothermal conditions afforded the electroneutral complex (Co3(SC3H7)s(CO)4], which contains a triangle of cobalt atoms. Its structure is shown in Fig. 16. 

Some thiolate metal complexes, unlike the oxygen complexes referred to above are powerful antioxidants (see Chapter 1) and undergo inversion to prooxidant metal ions in sunlight. The iron, manganese, cobalt, vanadium and cerium dithiocarbamates (II) are typical examples of such restrained prooxidants. 

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