- Dithiolene
A 1,2-dithiolene is an unsaturated bidentate
ligand wherein the two donor atoms aresulfur . These ligands readily form complexes by co-ordinating tometal centres "via" the sulfur atoms; such complexes are often referred to as "metallodithiolenes" or "dithiolene complexes". [Karlin, K. D.; Stiefel, E. I., Eds. “Progress in Inorganic Chemistry, Dithiolene Chemistry: Synthesis, Properties, and Applications” Wiley-Interscience: New York, 2003. ISBN 0-471-37829-1]Dithiolenes have been intensely studied since the 1960's, when they were first popularized by G. N. Schrauzer, who prepared Ni(S2C2Ph2)2 by the reaction of nickel sulfide and
diphenylacetylene . [cite journal | author = Schrauzer, G. N.; Mayweg, V. | title = Reaction of Piphenylacetylene with Ni Sulfides | journal =J. Am. Chem. Soc. | year = 1962 | volume = 84 | pages = 3221 | doi = 10.1021/ja00875a061] A large number of such complexes have been described with regards to their structural, spectroscopic, and electrochemical properties. Research on dithiolenes intensified with the discovery that most molybedenum-containing and tungsten-containing proteins contain dithiolene ligands, the so-calledmolybdopterin cofactor. [cite journal | author = Romão, M. J.; Archer, M.; Moura, I.; Moura, J. J. G.; Legall, J.; Engh, R.; Schneider, M.; Hof, P. and Huber, R. | title = Crystal Structure of the Xanthine Oxidase-Related Aldehyde Oxido-Reductase from D-Gigas | journal = Science | year = 1995 | volume = 270 | pages = 1170–1176 | doi = 10.1126/science.270.5239.1170 | pmid = 7502041]Background and nomenclature
Early studies on dithiolene ligands, although not called by that name until the the 1960's, [cite journal | author = McCleverty, J. A. | title = Metal 1,2-Dithiolene and Related Complexes | journal =
Progress Inorganic Chemistry | year = 1968 | volume = 10 | pages = 49–221 | doi = 10.1002/9780470166116.ch2] focused on the quinoxaline-2,3-dithiolates and 3,4-toluenedithiolates, which form brightly colored precipitates with several metal centres. Such species were originally of interest in analytical chemistry. Dithiolenes lacking benzene backbones represented an important development of the area, especially maleonitrile-2,3-ditholate ("mnt"), (NC)2C2S22-, and ethylenedithiolene, H2C2S22-.Electronic structure
The electronic structure of dithiolene complexes has been the subject of intense study because of their unusual redox properties.Ligands can be described as "innocent" if they are known, or predicted, to adopt a set oxidation state and thus allow the oxidation state of the metal centre to be defined. Dithiolene ligands, however, are thought to exist in two
oxidation states separated by a two-electronredox process, the dianionic "ene-1,2-dithiolate" and the neutral "1,2-dithioketone," which, when complexed to a metal centre, results in a system whereby theoxidation state of theligand (and therefore the metal centre) cannot be defined by conventional means. Such ligands are therefore referred to as "non-innocent".1,2-di
thione s have not been characterized crystallographically. Dithioketones, more so thanthioketone s, are expected to be unstable with respect to self-condensation to giveoligomers .The two substituents on the backbone of the dithiolene ligand, R and R', affect the properties of the resulting metal complex in the expected way. Long chains confer solubility in less polar solvents. Electron acceptors (e.g. CN, CO2Me) stabilize reduced and anionic complexes. Derivatives are known where the substituents are the same, symmetrical dithiolenes (R = R') are more common than unsymmetrical.
Due to the delocalized nature of dithiolenes, metal dithiolenes often exist in multiple oxidation states. In oxidized dithiolene complexes have relatively more 1,2-dithioketone character. In reduced complexes, the ligand assumes more ene-1,2-dithiolate character. These descriptions are evaluated by examination of differences in C-C and C-S bond distances.
These limiting structures do not represent a true description of the actual structure of the complex, the true structure lies somewhere between. Reflecting the impossiblility to provide an unequivocal description of the structure, McCleverty introduced the term 'dithiolene' to give a general name for the ligand that does not specify a particular oxidations state. This suggestion was generally accepted, and 'dithiolene' is now a universally accepted term.
Preparation
From alkenedithiolates
Most dithiolene complexes are prepared by reaction of alkali metal salts of 1,2-alkenedithiolates with metal halides. A common alkenedithiolate is mnt2-, which forms a very stable Ni(II) complex: [cite journal | author =
R. H. Holm , A. Davison | title = Metal Complexes Derived from cis-1,2-Dicyano-1,2-Ethylenedithiolate and Bis(trifluoromethyl)-1,2-Dithiete" | journal =Inorg. Synth. | year = 1967 | volume = 10 | pages = 8–26 | doi = 10.1002/9780470132418.ch3] : Ni2+ + 2 (NC)2C2S22- → Ni [S2C2(CN)2] 22-This red-colored complex is often used as a standard for electrochemical studies.For more electron-rich alkenedithiolates, the dianion is generated in situ, treated with the metal salt, and the product is often air-oxidized:: cis-H2C2(SCH2Ph)2 + 4 Na → cis-H2C2(SNa)2 + 2 NaCH2Ph: NiCl2 + 2 cis-H2C2(SNa)2 → Na2 [Ni(S2C2H2)2] + 2 NaCl: [Ni(S2C2H2)2] 2- → Ni(S2C2H2)2 + 2 e-
From acyloins
An early and still powerful method for the synthesis of dithiolenes entails the reaction of α-hydroxyketones,
acyloin s, with P4S10 followed by hydrolysis and treatment of the ill-defined mixture with metal salts. This method is used to prepare Ni [S2C2Ar2] 2 (Ar = aryl).From dithietes
Although 1,2-dithiones are extremely rare and thus not useful precursors, their valence isomer, the
dithiete s are occasionally used. Dithietes have even been characterized crystallographically. [cite journal | author = Donahue, J. P. and Holm, R. H. | title = 3,4-Bis(1-Adamantyl)-1,2-Dithiete: the First Structurally Characterized Dithiete Unsupported by a Ring or Benzenoid Frame | journal =Acta Crystallographica Section C : Crystal Structure Communications | year = 1998 | volume = C54 | pages = 1175–1178 | doi = 10.1107/S0108270198002935] Probably the most important dithiete is (CF3)2C2S2, prepared from the reaction of elementalsulfur andhexafluoro-2-butyne . This electrophilic reagent oxidatively adds to many low valent metals to give bis- and tris(dithiolene) complexes.: Mo(CO)6 + 3 1,2-(CF3)2C2S2 → [(CF3)2C2S2] 3Mo + 6 CO: Ni(CO)4 + 2 1,2-(CF3)2C2S2 → [(CF3)2C2S2] 2Ni + 4 COBy reactions of metal sulfides with alkynes
Species of the type Ni [S2C2Ar2] 2 were first prepared by reactions of nickel sulfides with
diphenylacetylene . More modern versions of this method entail the reaction of electrophilic acetylenes with well defined polysulfido complexes.tructural characteristics
Dithiolene complexes can be found where the metal centre is coordinated by one, two, or three dithiolene ligands. The tris(dithiolene) complexes were the first examples of trigonal prismatic geometry in coordination chemistry. One example is Mo(S2C2Ph2)3. Similar structures have been observed for several other metals. [cite journal | author = Eisenberg, R. and Gray, H. B. | title = Trigonal-prismatic coordination. Crystal and Molecular Structure of Tris (cis-1,2-diphenylethylene-1,2-dithiolato)vanadium | journal =
Inorg. Chem. | year = 1967 | volume = 6 | pages = 1844–9 | doi = 10.1021/ic50056a018]Applications
Applications of 1,2-dithiolene complexes have been disccussed in the context of conductivity,
magnetism , andnonlinear optics . Relatively few dithiolene complexes have been commercialized for use as dyes in laser applications.References
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