Sulfur complexes synthesis

The overall sequence occurs under nearly neutral conditions at room temperature and was shown to be an efficient tool for an oxidative desulfurization step required in sulfur-mediated synthesis of complex molecules such as methynolide and cytochalasin [253]. 

A general procedure for the synthesis of metal-sulfur complexes does not exist. However, the affinity between sulfur and the transition metals can be easily observed considering the fact that such very different reagents as, for instance, H2S, S8, S2, SCN-, S2Oj, SO2-, RNSNR or RSH may be the precursors of sulfide ligands, apart from S2 itself. Very little is known, however, about the reaction pathways. 

Only relatively few examples exist for complexes of transition metals with Se-containing dithio-lene-like ligands and those containing Te are unknown.Their synthesis generally follows the routes established for the sulfur complexes. 

Well-defined nickel-sulfur complexes that enable a stepwise combination of CO, alkyl, and thiol groups to give thioesters can be anticipated to yield deeper insight into the molecular mechanism of the acetyl-CoA synthesis (142, 149). The complex [Ni(C3Me2—S4)] afforded an example for such a thioester synthesis. In principle, it is even catalytic and Scheme 36 summarizes the individual steps (10). 

Chapter 1 deals with synthesis, where we learn that there are many ways to make dithiolene complexes, either from preformed ligands or through the chemical reactivity of bound sulfur species. Synthesis is at the core of most of the coordination chemistry that has been done on dithiolene complexes. Chapter 2 deals with structures and structural trends of the most common simple dithiolene complexes. Indeed, it was the square-planar nature of most late transition metal bis(dithiolene) complexes and the unprecedented trigonal-prismatic six-coordination of some of the tris(dithiolene) complexes that was one of three major drivers for early work in the held. 

The synthesis of (//-C5H5)Mo(NO)(CO)2 was first reported in 1956, and a revised procedure has been outlined. The compound is a particularly useful precursor for the preparation of a variety of sulfur complexes, carbene deriv-atives, and halides [(//-C5H5)Mo(NO)X2]2 (X = Cl, Br, F. ). The halides, especially when X = I, are important intermediates in the formation oftheste-reochemically nonrigid (CsH5)2Mo(NO)I and (C5H5)3Mo(NO) compounds. ... 

Methylbromoarsines, synthesis 26 Vanadium(III) fluoride, synthesis 27 Sulfur(IV) fluoride, synthesis 33 Peroxydisulfuryl difluoride, synthesis 34 Trichloro(tripyridine)chromium(III), synthesis 36 Tris(3-bromoacetylacetonato)chromium(III), synthesis 37 Trichloro(tripyridine)molybdenum(III), synthesis 39 Uranyl chloride 1-hydrate, synthesis 41 Rhenium(III) iodide, synthesis 50 Potassium hexachlororhenate(IV) and potassium hexa-bromorhenate(IV), synthesis 51 Iron-labeled cyclopentadienyl iron complexes, synthesis 54 Inner complexes of cobalt(III) with diethylenetriamine, synthesis 56... 

Toward Novel Organic Synthesis on Multi-metallic Centers Synthesis and Reactivities of Polynuclear Transition-Metal-Sulfur Complexes. 

Olah, G.A. and YD. Vankar. 1978. Synthetic methods and reactions. 52. Preparation of nitriles from aldoximes via dehydration with trimethylamine/sulfur dioxide complex. Synthesis 9 702-703. 

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