Synthesis and Spectroscopic Investigations of New Linear Heterobimetallic Clusters

Z. Naturforsch. 55 b, 238-242 (2000); received Oktober 10, 1999 IR Data, Chalcogenides, Molybdenum, Tungsten Red-brown crystals of a new bis(thiomolybdate) complex [Me4N]3[(MoOS3)2Ag] were formed at room temperature through the reaction of a solution of [Me4N]2[MoOS3] in MeCN with solid AgCN. They are monoclinic, space group P2i/c with unit cell parameters a = 16.662(9), b = 9.464(3), c = 17.890(8) A, /3 = 101.87(2)°, Z = 4. The crystal structure was determined from single crystal diffractometer data (MoKa-radiation) and refined to R = 0.044 (3614 reflections, 236 variable parameters). The structure is characterized by trinuclear complex anions, [(MoOS3)2Ag]3~. According to Weissenberg investigations the homologous tungsten compound is isostructural. The infrared spectrum of the molybdenum complex (KBr powder) shows absorption bands at 884 (vs) and 871 (w) cm-1 (terminal i/(Mo-0)), 483 (vs) cm-1 (terminal i/(Mo-S)), 451 (vs), and 435 (w) cm-1 (bridging i/(Mo-S)). The tungsten complex showed bands at 901 (vs) cm-1 (terminal ^(W-O)), 478 (vs) cm-1 (terminal u(W-S)), and 435 (vs) cm-1 (bridging ^(W-S)). The anionic mass spectra shows molecular ion peaks at m/z 524 and 700 for [(MoOS3)2Ag]_ and [(WOS3)2Ag]~, respectively, as well as peaks for other fragments.