ABSTRACT
Coordination of two dithiafulvenyldiphenylphosphines on a Mo(CO)(4) fragment allows a carbon-carbon bond formation upon oxidation, leading to a novel type of metallacycle substituted by a redox active vinylogous tetrathiafulvalene.
ABSTRACT
Cyclic vinylogous tetrathiafulvalenes (TTFs) where the two dithiole rings are linked through the outer sulfur atoms with an alkyl chain of various lengths were synthesized by oxidative intramolecular coupling of bis(dithiafulvenes). Upon oxidation, these systems exhibit large molecular movements associated with electron transfers. Their electrochemical behaviors were investigated together with the X-ray crystallographic structures of several derivatives and compared with molecular geometry calculations. Dependent on the length of the alkyl chain, either a stretch or a clip movement can be observed. These conformational modifications were found to be fast and fully reversible and required only low oxidation potentials. The movements seem to be almost insensitive to the nature of the substituents or its steric hindrance on the central conjugated spacer.
ABSTRACT
The synthesis of a ligand containing as an electroactive core a tetrathiafulvalene moiety, 3-[3-(diphenylphosphino)propylthio]-3',4,4'-trimethyl-tetrathiafulvalene, is reported. Its versatile ability to act as a bidentate or a monodentate ligand, as demonstrated by the metal carbonyl complexes obtained, is described. The novel cis-Mo(CO)(4)(P-TTF)(2) 4 and cis-W(CO)(4)(P,S-TTF) 6 complexes have been characterized by X-ray diffraction analyses and cyclic voltammetry measurements. Within complex 4, no significant influence of the two electroactive ligands on the molybdenum center was detected, whereas, in complex 6, a weak influence of the TTF redox-active core can be observed on the redox behavior of the metal center.
