Tungsten sulfide complexes

The catalytic cycle with the W04 catalysts is thought to involve the generation of tungsten peroxy complexes (Scheme 8.1). These react fast with the sulfide with transfer of an oxygen to give the sulfoxide. 

The complexity of the oxide-sulfide transformation leads to some difficulties in sulfiding, for example, tungsten sulfide or other sulfide phases if in interaction with a nonoptimized support. In this respect, the use of thiosalts and more particularly thiomolybdates and thiotungstates represents an interesting alternative to the classical sulfidation of oxides. Ammonium thiomolybdate (NH)2MoS4 (ATM) was first synthesized by Kruss [53] in 1884. Later, Alonso et al. described an improved way of preparing ATM [54]. The synthesis of ammonivun thiotungstate (ATT)... 

Pyridine complexes of Pd- and Pt-pincer ligands are also suitable substrates for olefin metathesis [116]. The first-generation catalyst 9 efficiently mediates the RCM of diallylphosphines and diallyl sulfide when the heteroatom is com-plexed by a cationic [C5H5(NO)(PPh3)Re] moiety [117]. This principle has been exploited in the same study for tungsten, rhodium, and platinum complexes. 

Lewis Bases. A variety of other ligands have been studied, but with only a few of the transition metals. There is still a lot of room for scoping work in this direction. Other reactant systems reported are ammoni a(2e), methanol (3h), and hydrogen sulfide(3b) with iron, and benzene with tungsten (Tf) and plati num(3a). In a qualitative sense all of these reactions appear to occur at, or near gas kinetic rates without distinct size selectivity. The ammonia chemisorbs on each collision with no size selective behavior. These complexes have lower ionization potential indicative of the donor type ligands. Saturation studies have indicated a variety of absorption sites on a single size cluster(51). 

C H402, Acetic acid palladium complex, 26 208 tungsten complex, 26 224 C2H7PS, Phosphine sulfide, dimethyl-manganese complex, 26 162 C H,N2, 1,2-Ethanediamine chromium complex, resolution of, 26 24, 27... 

There are also interesting complexes with sulfide bridging between gold(I) and tungsten(VI),... 

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