Manganese complexes sulfur ligands

Following our early studies (89, 90), we have recently investigated derivatives of manganese carbonyl obtained from reactions between Mn(CO)5X (X usually Br) and organic sulfur ligands (93). Manganese carbonyl chelate complexes are formed in which sulfur is covalently bonded to manganese, or forms a coordinate bond as an electron donor. 

The complex [Mn4(S2)2(CO)i5l contains two disulfide ligands and has been obtained by oxidation of [Mn2(SSnMe3)2(CO)8] " Similar to [Mn3(S2)2(CO)9(SH)] (see Chapter 1.10.5), the disulfide groups are coordinated in different coordination modes. Each manganese atom is coordinated pseudo-ociahedx Wy by six ligands, but the coordination spheres of the individual atoms differ with respect to the total number of sulfur ligands. Two of them are coordinated to three sulfur atoms, the other ones to two and one, respectively. The family of tetranuclear complexes... 

The reaction of Re(CO)5Br with PhCOSH gives the dimeric complex 30, where the thiocarboxyl sulfur atom is coordinated to the two rhenium atoms [99], whereas heating with cesium thiobenzoate in ethanol leads to the anion complexes 31 in which the S-thiobenzoato ligands are triply bridged to the two rhenium atoms [213]. In addition, reaction with Cs2(SOC-COS) affords (OC)5Re(SOC-COS)Re(CO)5 [326], the structure of which resembles that of the corresponding manganese complex 28. 

Manganese(tl) complexes,, 3, 9-82 acctylacetonates, 48 acetylides, 14 alcohols, 37 alkoxides, 37 alkyl phosphines, 13 alkyls, 12 amides, 15, 16 amine oxides, 39 amines, 16 amino acids, 43, 62 sulfur containing, 70 ammines, 15 antimony ligands, 31-34 arsenates, 4,5, 46 arsenic ligands, 31-34 arsenic oxides, 39 aryls, 12, 14 azides, 22 binary alkyls, 13 bipyridyl, 24, 25 anions, 25... 

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