Kubanartige Molybdän-Halogen-Schwefel-Clusterdithiophosphinate / Cubane Type Molybdenum-Halogen-Sulfur Clusterdithiophosphinates

Georg Borgs, Helmut Keck, Wilhelm Kuchen, Dietrich Mootz, René Wiskemann, Hartmut Wunderlich
1991 Zeitschrift für Naturforschung. B, A journal of chemical sciences  
Diamagnetic clusters [Mo3X-μ-(S2)3-μ3(S)(R2PS2)3] 2-4 (2: X = Cl; 3: X = Br; 4: X = I; 2-4: a: R = Et; b: R = Pr; c: R = Bu) are conveniently obtained by reaction of [Mo3S7(R2PS2)3]+(R2PS2)- 1 either with alkyl halides RX or with tetraalkylammonium halides R4NX. Between halogen X and one of the S atoms of each disulfido bridge there exist bonds which seem to be mainly of covalent character. Thus X is incorporated into the cluster core leading to a cubane type structure. [Mo3ClS7(Et2PS2)3] forms
more » ... lS7(Et2PS2)3] forms orthorhombic crystals with space group Pnma, Z = 4, a = 1931.9(7), b = 1551.2(6), c = 1286.5(4) pm. Isostructural substructures of 3b, 4a and 4b (space group P21) were also studied. All these cluster molecules reveal similar core geometries with distances S—Cl 239.4(4), S—Br 305(1) and S—I 322.5(3) pm much less than the sum of the van der Waals radii. The results of structural and spectroscopic investigations are discussed.
doi:10.1515/znb-1991-1112 fatcat:66x4l42f3vfcpa47o27godhk5u