Metal sulfur dioxide complex
Metal sulfur dioxide complexes are complexes that contain sulfur dioxide, SO2, bonded to a transition metal. Such compounds are common but are mainly of theoretical interest. Historically, the study of these compounds has provided insights into the mechanisms of migratory insertion reactions in organometallic chemistry.
Sulfur dioxide forms complexes with many transition metals. For the most stable complex the metal is in oxidation state 0 or +1.
In most cases SO2 binds in monodentate fashion, attaching to the metal through sulfur. Such complexes are further subdivided according to the planarity or pyramidalization at sulfur. The various bonding modes are:
More exotic bonding modes are known for clusters.
Complexes of the transition metals are usually generated simply by treating the appropriate metal complex with SO2. The adducts are often weak. In some cases, SO2 displaces other ligands.
A large number of labile O-bonded SO2 complexes arise from the oxidation of a suspension of the metals in liquid SO2, an excellent solvent.
The main reaction of sulfur dioxide promoted by transition metals is its reduction by hydrogen sulfide. Known as the Claus process, this reaction is conducted on a large scale as a way to remove hydrogen sulfide that arises in hydrotreating processes in refineries.
Of academic interest, SO2 acts like a Lewis acid towards the alkyl ligand. The pathway for the insertion of SO2 into metal alkyl bond begins with attack of the alkyl nucleophile on the sulfur centre in SO2. The "insertion" proceed the sulfur dioxide between the metal and the alkyl ligand leads to the O, O'-sulphinate. Alternatively an O-sulphinate can arise. Both of these intermediates commonly convert to an S-sulphinate.S-sulphinate has sulfur–oxygen stretching frequencies from 1250–1000 cm−1 and 1100–1000 cm−1. The O, O'-sulphinate and O-sulphinate are difficult to distinguish as they have stretching frequencies from 1085–1050 cm−1 and 1000–820 cm−1 or lower. The pathway involving the O, O' sulphinate can generally be ruled out if the original metal complex fulfilled the 18-electron rule because the two metal–oxygen bonds would exceed the 18 electron rule. The pathway by which SO2 inserts into a square planar alkyl complexes involves the formation of an adduct. Thereafter, the alkyl ligand migrates to the SO2.
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