62024-60-6Relevant articles and documents
Synthesis of unsymmetrically substituted TTF derivatives via the 'phosphonate way'. Some investigations on the scope of the method
Cristau,Darviche,Babonneau,Fabre,Torreilles
, p. 13029 - 13036 (1999)
The scope and limitations of the synthesis of unsymmetrically substituted TTF derivatives via the 'phosphonate way' was investigated using as precursors 1.3-dithiol-2-yl-phosphonates and 1.3-dithiol-2-yliden iminium salts with various substituents on the dithiole cycles. Except for the un- or monosubstituted phosphonates, the one-pot procedure proves to be general and affords in all cases a significant improvement in the overall yields in TTF derivatives. The study has shown also that the formation of the intermediate adducts occurs in high yield, but their transformation into TTF derivatives, in presence of anhydrous acetic acid, is strongly sensitive to the nature of the various substituents, particularly on the iminium part.
Oxidation of phosphines containing two or three tetrathiafulvalene (TTF) or o-dimethyl-TTF moieties. Evidence for formation of radical polycations
Gerson, Fabian,Lamprecht, Axel,Fourmigue, Marc
, p. 1409 - 1414 (2007/10/03)
Stepwise oxidation of tetrathiafulvalenyl(diphenyl)phosphine (1), 4′,5′-dimethyltetrathiafulvalen-4-yl(diphenyl)phosphine (1a), bis(tetrathiafulvalenyl)phenylphosphine (2), bis(4′,5′-dimethyl- tetrathiafulvalen-4-yl)phenylphosphine (2a), tris(tetrathiafulvalenyl)phosphine (3) and tris(4′,5′-dimethyltetrathiafulvalen-4-yl)phosphine (3a) was followed by EPR and ENDOR spectroscopy, and cyclic voltammetry. Each of the tetrathiafulvalene (TTF) or 4,5-dimethyltetrathiafulvalene (o-DMTTF) moieties in 1-3a donates two electrons, so that exhaustive oxidation at potentials below 1 V (vs. SCE) leads to the dications 12+ or 1a2+, the tetracations 24+ or 2a4+ and the hexacations 3 6+ or 3a6+. In 2, 2a, 3 and 3a, the electrons are removed one-by-one from different TTF or o-DMTTF moleties. In the initially formed radical cations 2.+, 2.+, 3.+ and 3a .+, the electron hole is delocalized over all TTF or o-DMTTF moieties, two in 2.+ or 2a.+ and three in 3.+ or 3a.+ .On the other hand, in paramagnetic species produced by further oxidation and also giving rise to well defined EPR and ENDOR spectra, the unpaired electron appears on the hyperfine time-scale as localized in only one donor moiety. These species are supposed to be the radical trications 2 .3+ or 2a.3+ and the radical pentacations 3.5+ or 3a.5+. The intermediately occurring dications 22+ or 2a2+ and 32+ or 3a2+, as well as the tetracations 34+ or 3a4+, should have a triplet ground-state, while the trications 33+ or 3a3+ are expected to be quartet species.