Synthesis, structural characterization, and properties of the [Mo2O2S9]2- thio anion and the [Mo4O4S18]2-, [Mo2O2S8(SCH3)]-, and [Mo2O2S8Cl]- derivatives

Abstract

ChemInform Abstract The compound (V) contains a mixture of (Mo2O2S10)2-and (Mo2O2S9)2-anions. Oxidative coupling of the latter anion affords the Mo(VI) linear tetramer (VIII), which crystallizes in space group P1 with Z=2. Reaction of (V) with NiCl2 yields the new chloro derivative (X) ( P21/n, Z=4) as a result of ligand exchange. The nucleophilicity of (Mo2O2S9)2-is demonstrated in its reaction with MeI, which gives the methanethiolato-bridged derivative (VI). Both (V) and (VI) crystallize in the space group P21/c with Z=4. The structures of (V), (VI), (VIII), and (X) contain Mo(VI) ions with pseudo-pentagonal bipyramidal environments.

Reactivity and kinetic studies of (NH4)2(MoS4) in acidic aqueous solution: Possible relevance to the angiostatic function of the MoS42- ligand

“…Mo 2 S 2À 8 + 2e À ). There was no evidence of Mo 2 S 2À 7 formation in this study to support a proton-activated dimerization of MoS 2À 4 to S 3 Mo VI (l-S) Mo VI S 3 , as a transition state to S 2 Mo VI (l-S) 2 Mo IV S(S 2 ), before forming Mo 2 S 2À 8 [37,59]. On the other hand, the proposal in this paper for the formation of H 2 alongside the (poly)nuclear thiomolybdate product seems to gain support from the literature [33].…”

“…The other isolated fractions were not pure, nevertheless, matching the measured UV-vis and IR-data to those of known polynuclear (oxo)thiomolybdates [34,[36][37][38][39][40] helped in the assignment of the dominant anions in the isolated crude products as observed by ESMS. For instance, the ESMS spectrum of the isolate IIB indicated two main isotopic peak patterns; a 100% relative intensity isotopic peak envelop most intense at m/z 231.8 (z = 2), and a 51.6% relative intensity peak most intense at m/z 239.…”

“…From IR measurements, detection of dominant characteristic vibrations of polynuclear thio-and oxothio-molybdates as reported and assigned in the literature [34,[36][37][38] (i.e. m (S-S) br , m (S-S) t , Mo-S, Mo-S b , Mo-S 2 , Mo-S 4 , Mo@S t , Mo@O t , etc.)…”

“…The isolated fraction (IIB) was not pure and we could not purify it further. The dominant anions were however identified by the ESMS data complemented by matching the measured UV-vis, IR and Raman data to those of known polynuclear (oxo)thiomolybdates [34,[36][37][38][39][40]. The ESMS spectrum of the isolate IIB indicated two main isotopic peak patterns; a 100% relative intensity isotopic peak envelop most intense at m/z 231.8 (z = 2), which was assigned to Mo 2 O 3 S 2À 7 , and a 51.6% The basis for the ESMS peak assignments is discussed in the results section.…”

Synthesis, Structure, and Behavior in Solution of the Dawson Thio Derivative [(P2W17O61)2(H4Mo4S4O6)]16–

“…[36] The conversion of the anti into the syn conformation is H 3 O + -catalyzed and thus the presence of the anti conformation in water containing solvent is likely not expected. [34] These features rather argue for a syn-syn interaction, depicted in Figure 2a, without any change in the original syn conformation of the dinuclear precursor through the assembling process.…”