Reaction between Vanadium Trichloride Oxide and Hydrogen Sulfide

Abstract

The details of the reaction between vanadium trichloride oxide and hydrogen sulfide were examined at 20 and 60 °C. The main products by the reaction were vanadium dichloride oxide, sulfur, and hydrogen chloride. In addition to these products, small amounts of vanadium trichloride, vanadium tetrachloride, disulfur dichloride, and sulfur dioxide were formed. The formations of the above-mentioned reaction products can be explained as follows: The first stage is the reaction between vanadium trichloride oxide and hydrogen sulfide, 2VOCl3(1)+H2S(g)→2VOCl2(s)+S(s)+2HCl(g). Then the resulting sulfur reacts with the unreacted vanadium trichloride oxide, 2VOCl3(1)+2S(s)→2VOCl2(s)+S2Cl2(1). The resulting disulfur dichloride subsequently reacts with the unreacted vanadium trichloride oxide, 2VOCl3(1)+S2Cl2(1)→2VCl4(1)+S(s)+SO2(g). The resulting vanadium tetrachloride reacts with the sulfur formed during the reaction, 2VCl4(1)+2S(s)→2VCl3(s)+S2Cl2(1), and also reacts with hydrogen sulfide, 2VCl4(1)+H2S(g)→2VCl3(s)+S(s)+2HCl(g).

Infrared Matrix Isolation and Density Functional Theory Study of Intermediates in the Reactions of OVCl3 and CrCl2O2 with H2O

“…High-valent transition metal oxo compounds, including OVCl 3 and CrCl 2 O 2 , are very strong oxidizing agents and are known to oxidize a wide range of organic substrates. This oxidizing power has applications in catalysis as well as in organic synthesis. , However, very little is known about the reaction of these reagents with H 2 O, despite its ubiquitous presence in nature. A single drop of either reagent will fume vigorously in the atmosphere, generating HCl and additional products.…”

Matrix Isolation Study of the Thermal and Photochemical Reaction of OVCl3 with NH3: Spectroscopic and Theoretical Characterization of Cl2V(O)NH2

“…High valent transition metal oxo compounds, including OVCl 3 and CrCl 2 O 2 , have been used on many occasions as potent yet selective oxidizing agents in organic synthesis. , However, the high reactivity of these systems have prevented researchers in many cases from determing the mechanistic details of these oxidation reactions. In contrast, several detailed theoretical studies − have explored such systems and postulated the existence of multiple intermediates in model systems involving high valent transition metal oxo compounds.…”

“…High valent transition metal oxo compounds, including OVCl 3 and CrCl 2 O 2 , have been used on many occasions as potent yet selective oxidizing agents in organic synthesis. 1,2 However, the high reactivity of these systems have prevented researchers in many cases from determing the mechanistic details of these oxidation reactions. In contrast, several detailed theoretical studies [3][4][5][6][7] have explored such systems and postulated the existence of multiple intermediates in model systems involving high valent transition metal oxo compounds.…”

Matrix Isolation and Density Functional Study of the Reaction of OVCl3 with CH3OH: Synthesis and Characterization of Cl2V(O)OCH3

“…High valent transition metal oxo compounds form a class of very strong oxidizing agents toward a wide range of organic substrates. Vanadium oxytrichloride, Cl 3 VO, is a prototypical member of this group, vigorously oxidizing many organic reagents. , However, very little is known experimentally concerning the mechanism of these reactions, including the identity of key intermediates. On the other hand, a series of theoretical studies have been carried out in recent years, with the aim of providing a better understanding of the mechanisms, intermediates, and energetics in reactions of transition metal oxo compounds. − …”