The coordination chemistry of small sulfur-containing molecules: a personal perspective

Abstract

The sulfur oxides SO, SO₂ and SO₃, and thioformaldehyde H₂C=S and its oxides H₂C=SO and H₂C=SO₂ form stable coordination compounds with a range of transition metals. The complexes have a rich chemistry which differs markedly from that of the free ligands. Typical reactions involve electrophilic additions, nucleophilic additions and cycloadditions. The complexes can be used as synthons to incorporate these small molecules as building blocks into larger structures.

Isolation and Characterization of a Non‐Rigid Hexamethylbenzene–SO2+ Complex

“…[17] Interestingly, SO can be stabilized as a ligand in the coordination sphere of metal complexes. [16,[18][19] In general, the μ 2 bridging mode [20] is much more often observed than SO as a terminal [21] or μ 3 bridging ligand. [22] Recently, adduct formation of SO with carbenes has been reported.…”

Isolierung und Charakterisierung eines nicht‐starren Hexamethylbenzol‐SO2+‐Komplexes

“…[17] Interessanterweise kann SO als Ligand in der Koordinationssphäre von Metallen stabilisiert werden. [16,18,19] m 2 -Verbrückung [20] wird fürS O-Liganden häufiger beobachtet als terminale Koordination [21] oder m 3 -Verbrückung. [22] Kürzlich wurde auch über Addukte von SO mit Carbenen berichtet.…”

Dithionite and sulfinate complexes from the reaction of SO2with decamethylsamarocene

“…For example, it is used in the production of sulfuric acid. [2][3][4] The vast majority of reported compounds are based on electron-rich transition metals. 1 Besides the synthesis of sulfur-containing chemicals such as sulfuric acid, sulfur dioxide is a wellestablished ligand in coordination chemistry.…”

“…1 Industrially, sulfur dioxide is produced by combustion of elemental sulfur or by oxidation of metal sulfides. [2][3][4][5] Besides the oxidation of sulfur dioxide to sulfur trioxide for the production of sulfuric acid, 6 the reduction of sulfur dioxide to elemental sulfur (Claus process) 7 or to sodium dithionite 8 are also well-established industrial processes. [2][3][4] The vast majority of reported compounds are based on electron-rich transition metals.…”