The Coordination Chemistry of Sulfoxides

THE COORDINATION CHEMISTRY OF SULFOXIDES WITH TRANSITION METALS... 

The coordination chemistry of sulfoxides with transition metals is a much-studied topic.87 Academic interest has often centred on their ambidentate donor ability, while dimethyl sulfoxide (DMSO) is of intrinsic importance as one of the most effective aprotic solvents known. Higher sulfoxides have found application in the extraction of metals during refining processes and some potential in the separation of platinum group metals has been noted.88... 

The Coordination Chemistry of Sulfoxides with Transition Metals J. A. Davies... 

This review is intended as an account of the coordination chemistry of both dimethyl sulfoxide and the higher sulfoxides, with particular reference to the mode of bonding and the extent to which this affects the chemistry of transition-metal sulfoxide complexes. No attempt has been made to provide an exhaustive listing of all known sulfoxide complexes, many of which contain coordinated sulfoxide moieties only coincidentally to their other important functions. 

Comprehensive literature reviews on coordination of sulfoxides have appeared. Reynolds has surveyed the chemical and physical properties of DMSO and its interactions with metals up to 1968. Davies5 has covered the coordination chemistry of transition elements with the full range of sulfoxides up to 1979, including a discussion of the physical methods applied. 

Coordination of mercurial species is certainly involved in several of these processes. Although the strictly inorganic compounds of mercury form well-defined coordination complexes with amines, phosphines, sulfoxides, phosphine oxides, and amine oxides, particularly when a noncoordinating gegenion for mercury is employed, coordination numbers up to six having been observed (56), the coordination chemistry of organometallic derivatives of mercury is just developing (87-89). 

Acid-base strength in MejSO The chemistry of MejSO (general) Coordination compounds of sulfoxides The chemistry of MejSO (inorganic)... 

The heavier chalcogens are more prone towards secondary interactions than sulfur. In particular, the chemistry of tellurium has numerous examples of intramolecular coordination in derivatives such as diazenes, Schiff bases, pyridines, amines, and carbonylic compounds. The oxidation state of the chalcogen is also influential sulfur(IV) centres engender stronger interactions than sulfur(II). For example, the thiazocine derivative 15.9 displays a S N distance that is markedly longer than that in the corresponding sulfoxide 15.10 (2.97 A V5. 2.75-2.83 A, respectively). ... 

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