166185-30-4Relevant academic research and scientific papers
Three-dimensional delocalization in tris(1,2-dithiolenes)
Argyropoulos, Dimitris,Lyris, Emmanuel,Mitsopoulou, Christiana A.,Katakis, Dimitris
, p. 615 - 621 (2007/10/03)
Tungsten tris(1,2-dithiolene) complexes [W(S2C2R1R6)(S2C 2R2R5)(S2C2R 3R4)] (R4,5,6 = H or Ph; R1,2,3 = para-substituted Ph), have been found to exhibit properties (1H NMR, UV/VIS, IR spectral) closely related to each other through Hammett constant σp+, indicating extensive delocalization and conjugation. A comparative study of complexes containing differently substituted dithiolenic rings showed that the electron delocalization is not confined within each dithiolenic ring separately, but involves all of them, i.e. it is three dimensional. This is further supported by a NMR and/or UV/VIS study of the effect of water and acid on the dimethylamine derivative. The oxidation number was assigned by recording the NMR spectra of the metal nuclei; the metals have effectively been stripped of their valence electrons; which are placed on the ligands. The non-planar 'aromaticity' of the dithiolenes differs from the familiar flat organic aromaticity since it involves mixing of σ and π bonding.
Synthesis, Cyclic Voltammetric and Electrospray Mass Spectrometric Studies of a Series of Tris-Substituted 1,2-Dithiolene Complexes of Tungstenand Molybdenum
Falaras, Polycarpos,Mitsopoulou, Christine-Anne,Argyropoulos, Dimitris,Lyris, Emmanuel,Psaroudakis, Nikos,et al.
, p. 4536 - 4542 (2008/10/08)
Ten new nonsymmetric dithiolenes of the general formula [RR'(C2S2)]3M were synthesized, from the corresponding 1,3-dithiol-2-ones, or from the corresponding mixed benzoins and tetraphosphorus decasulfide. The redox properties of these ten complexes together with those of the symmetric ones with R = R' = Ph and M = Mo or W, were investigated by cyclic voltammetry. Two processes were only observed, assigned to C C(1-) and C(1-) C(2-) (C the complex), for which the quasi-reversible E1/2 potentials are highly dependent on the nature of the central metal ion, and for the same metal on the nature of the ligand and on the substituents on the phenyl rings. The ease by which the complexes are reduced is most likely the reason they give ESMS (negative mode) spectra, in spite of the fact they are neutral in solution. The process of this reduction and the parameters affecting it are investigated and discussed.
