Transition Metal Polysulfides: Coordination Compounds with Purely Inorganic Chelate Ligands

Abstract

It has been long known that certain transition metal sulfides dissolve in aqueous ammonium polysulfide. Although it was assumed that they thereby formed metal polysulfides, attention was first paid to such compounds only a few years ago. In recent years a host of new complexes with polysulfido chelate ligands have been isolated and characterized. The complexes are of interest not only regarding their structure and reactivity but also in view of their potential uses; they can be used for the directed preparation of sulfur rings of a given size, and there are indications that they will find applications in catalysis.

Facets of early transition metal–sulfur chemistry: Metal–sulfur ligand redox, induced internal electron transfer, and the reactions of metal–sulfur complexes with alkynes

“…The vinyl sulfide (35), vinyl disulfide (36) and trithiolene (37) ligands are only sparsely represented due to their ready transformation into the more stable dithiolene ligand (38) [17]. The reactions of alkynes with metal complexes containing organosulfur ligands are generally more complicated, producing a number of intriguing species en route to dithiolene complexes.…”

“…Catenation and the interconversion of (poly)sulfido ligands at metal centers are two closely related aspects of metal-sulfur chemistry [17]. Early examples of these phenomena involve the various isomers of Cp 2 Mo 2 S 4 ((1)-(3)) ðCp ¼ g 5 -C 5 H À 5 Þ and the facile interconversion of the two known forms of [Mo 2 S 12 ] 2À , viz., [Mo 2 (l-S 2 ) 2 (S 2 ) 4 ] 2À (4) and [Mo 2 S 2 (l-S) 2 (S 4 ) 2 ] 2À (5).…”

Pentasulfide S52- as the First Tridentate Chelating Ligand in Ru(P(OE)3)3S5(E = Me and Et)

“…The average bond angles in the sulfur chain, 103.4°( S1-S2-S3), 99.9°(S2-S3-S4), and 102.5°(S3-S4-S5), are smaller than the normal S-S-S angle in R-S 8 (107°). 50 The Ru-S1-S2 bond angles are also smaller (104.7°) (av) than that reported for the RuSSRu core compounds, where the Ru-S-S is ca. 109°.…”

A Bulky Silylene Generated under Mild Conditions: Its Application to the Synthesis of Organosilicon Compounds

“…[47][48][49][50] However, there are only very few studies on silacyclic compounds containing chalcogens. We examined the synthesis of novel silacyclic compounds containing sulfur or selenium by the reactions of silylene 1 with elemental chalcogens and metallocene pentachalcogenides.…”