Transition metals dithiolenes

Chapter 2- Transition metal dithiolenes are versatile complexes eapable of a wide range of oxidation states, coordination geometries, and magnetie moments. As a eonsequence, these complexes have been widely studied as building bloeks for erystalline molecttlar materials. Particularly successful are the square-planar metal dithiolenes (Chart 1), from which materials have been produeed that exhibit condueting, magnetic, and nonlinear optieal properties, as well as supereonduetivity in some cases. " In their application to molecular- based... 

Two main synthetic routes are available for the preparation of dithiolenes in the first and most frequently used method, either the free ethylenedithiol or an appropriate salt of the ethylene-dithiolato ligand dianion is reacted with a metal salt to produce anions of the dithiolenes, which may or may not be subsequently oxidized to the neutral species the second one, applied so far only to transition metal dithiolenes, converts vicinal diketones into dithiodiketones and reacts these either with zerovalent metals to form dithiolenes directly or uses metal salts to arrive at cationic species, which are reduced to the neutral dithiolenes either during the reaction or in a subsequent step. 

Kirmse and coworkersl(rM 11 have shown the advantages of applying the ESR technique to transition metal dithiolenes (i) a large delocalization of the unpaired spin density giving rise to the... 

A mostly qualitative MO approach was used by Alvarez, Vicente and Hoffmann140 to interpret the regularities and irregularities in the dimerization and stacking of transition metal dithiolenes. While firm predictions could not be made, the balance between sulfur lone-pair repulsion, size and occupation of the metal d-orbitals and substitutent steric demand were pointed out. The coordination preference of ethylenetetrathiolate was determined to be of the 1,2-dithiolene type rather than the 1,1-dithiolene. This result was suggested to apply both to binuclear and polymeric species. 

Similar processes are observed with transition metal dithiolene complexes, in which a range of formal oxidation states of metal ions may be accommodated. In reality, this is... 

Rauchfuss, Thomas B., Synthesis of Transition Metal Dithiolenes. 52 1... 

This chapter discusses the synthesis of transition metal dithiolene complexes and is current to late 2002. Dithiolene chemistry has been reviewed several times previously, but this is the first review dedicated to synthetic aspects. Emphasis is placed on more contemporary methods, and the reader should consult the older reviews, especially those by Mueller-Westerhoff et al. (8) and McCleverty (9) for discussions of earlier literature. An effort was made to be comprehensive with respect to methods and the range of complexes examined, but the chemistry of metal dithiolenes is so vast that it is not practical to be exhaustive. 

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