TRIPLY BRIDGED BIMETALLIC THIOLATE COMPLEXES OF OXOMOLYBDENUM(V) - FORMATION AND STRUCTURE OF SECONDARY AMMONIUM-SALTS OF [(MU-OCH2CH2S-S,O) (MU-O) (OMO(OCH2CH2S))2]2-

Red compounds (BH+)2[Mo2O3(SCH2CH2O)3]2 (B = piperidine, morpholine, pyrrolidine) crystallize in moderate yield from reaction mixtures containing [MoOCl4(OH2)]- (or [Mo2O2(SCH2CH2O)2Cl3]-), HOCH2CH2SH, H2O, and B. Crystal-structure determination for the piperidinium compound reveals that [Mo2O3(SCH2CH2O)3]2- contains two multiply bonded Mo-Ot groups, each chelated by one -SCH2CH2O- ligand and bridged by three atoms, namely, sulfur (S3, cis to both Ot) and oxygen (OS3, approximately trans to both Ot) of the third SCH2CH2O- ligand and oxide (03, cis to both Ot). The coordination stereochemistry of each molybdenum atom is square pyramidal plus distant coordination (OS3) trans to apical Ot. One terminal -SCH2CH2O- ligand is cis, and the other trans, relative to the principal bridging atoms S3 and 03. Reactivity information and spectroscopic data are presented. Crystal data: a = 8.068 (1) Å,b= 19.904 (4) Å, c = 7.840 (1) Å, (3 = 102.61 (2)°, space group P21 Z = 2 × Mo2O6S3N2C16H36, dobsd = 1.73 g cm-3, 3080 observed reflections (Mo K α), R = 0.044, Rw = 0.051. © 1979, American Chemical Society. All rights reserved.