SYNTHESIS, STRUCTURE AND PROPERTIES OF DINUCLEAR AND TETRANUCLEAR MANGANESE(II) CHALCOGENOLATE COMPLEXES [MN-2(SC3H7)(6)](2-), [MN-2(SCH3)(6)](2-), [MN-2(CEC3H7)(6)](2-), [MN-4(SC3H7)(6)CL-4](2-) AND [MN-4(SEC3H7)(6)BR-4](2-)

Reaction of 1 : 3 molar ratio mixtures of MnCl2 and NaSR in MeCN/DMF g ave [Mn-2(SR)(6)](2-) (5a : R = Pr-i; 5b : R = Me), which were isolate d as [Me(4)N](2)[Mn-2(SR)(6)] (1a : R = Pr-i; 1b : R = Me). In a simil ar way, [Me(4)N](2)[Mn-2(SePri)(6)] (2) could be obtained. Compounds, Pa and 2 are isotypic. The metal-sulphur (selenium) cores of 5a, 5b an d [Mn-2(SePri)(6)](2-) (6) consist of two MnX(4) tetrahedra connected via a common edge. Structural similarities with related complexes are discussed. Reaction of Pa and 2 with two equivalents of MnCl2 and MnBr 2, respectively, in acetonitrile afforded [Me(4)N](2)[Mn-4(SPri)(6)Cl- 4] (3) and [Me(4)N](2)[Mn-4(SePri)(6)Br-4] (4), respectively. The comp lex anions [Mn-4(SPri)(6)Cl-4](2-) (7) and [Mn-4(SePri)(6)Br-4](2-) (8 ) are cage compounds with adamantane-type Mn(4)X(6) frameworks. The te trahedral coordination sphere of each manganese atom is completed by a terminally bonded halide ion. The structural properties of 7 and 8 ar e compared with other adamantane-like complexes. There is no evidence for the formation of manganese complexes with face-sharing MnX(4) unit s of formula [Mn-2(XR)(5)](-) (X = S, Se) yet. The solution UV-vis spe ctra of 1a, 2, 3 and 4 are reported.