Sulfur Oxides as Ligands in Coordination Compounds

Abstract

Donor molecules undergo dramatic changes in their chemical properties on coordination to a transit&-metal atom. Highly reactive species can be trapped and studied as ligands. Conversely, stable compounds can be activated to undergo novel reactions. Sulfur dioxide complexes have generally been studied from a structural viewpoint, their reactivity having been somewhat neglected. The unstable sulfur oxides SO, S20, and S202 are still often regarded as laboratory curiosities. Their successful stabilization in transition-metal complexes has now made them accessible to detailed study, in the course of which many relationships to the chemistry of SO2 complexes have become apparent.

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

“…Free SO even decomposes in high dilution in the gas phase within short time [16] but can be detected in interstellar space. [17] Interestingly, SO can be stabilized as a ligand in the coordination sphere of metal complexes.…”

“…[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.…”

Extensive theoretical study on electronically excited states and predissociation mechanisms of sulfur monoxide including spin–orbit coupling

“…In particular, the sulfur monoxide radical (SO) is a key intermediate in these combustion processes and, thus, is of vital importance in environmental chemistry. [1][2][3] In addition, SO is a compound of high reactivity, which could form complexes with transition metal, [4][5][6] and the singlet SO could help to determine the stereochemistry of cycloaddition reactions. and 6, at which the breaking-off of the m 0 5 2 and 3, bands happens, were revised to N 0 5 37 and 10, respectively.…”

Isotope exchange in disulfur monoxide-water charged complexes: A mass spectrometric and computational study

“…In the high-pressure limit the reaction proves to be a route to strongly bound sulfur-containing species. (J Am Soc Mass Spectrom 2007, 18, 1664 -1671) © 2007 American Society for Mass Spectrometry T he reactivity of the S 2 O˙ϩ ion is almost unknown compared to the valence-shell isoelectronic O 3 ·ϩ and SO 2 ·ϩ ions. The scant information available adds to the difficulty to prepare S 2 O˙ϩ by ionization of S 2 O, which is very unstable and not easily synthesizable with high purity [1].…”

“…The scant information available adds to the difficulty to prepare S 2 O˙ϩ by ionization of S 2 O, which is very unstable and not easily synthesizable with high purity [1]. Despite being unstable, S 2 O can be trapped in transition-metal complexes because of its -acceptor ability [2]. This interaction has also been theoretically investigated in charged complexes, such as [MnS 2 O] ϩ [3].…”