- Chemical reduction of 2,4,6-tricyano-1,3,5-triazine and 1,3,5-tricyanobenzene. Formation of novel 4,4′,6,6′-tetracyano-2,2′-bitriazine and its radical anion
-
Chemical reduction of 2,4,6-tricyano-1,3,5-triazine, TCT, results in the formation of an unstable radical anion that undergoes immediate dimerization at a ring carbon to form [C12N12]2-, [TCT]22-, characterized by a long 1.570 (4) A central C - C bond. [TCT]22- can decompose into the radical anion of 4,4′,6,6′-tetracyano-2,2′-bitriazine, [TCBT]-, the one-electron reduced form of planar (D2h) TCBT, which is also structurally characterized as the [TMPD][TCBT] charge-transfer complex (TMPD = N,N,N′,N′-tetramethyl-p-phenylenediamine) with a 1.492 (2) A central sp2 - sp2 C - C bond. Although crystals could not be obtained for the radical anion [TCBT]-, the electrochemistry (E° = +0.03 V), EPR (g = 2.003, 2A14N = 3.347 G, and 4A14N = 0.765 G and a line width of 0.24 G), and theoretical calculations support the formation of [TCBT]-. In addition, thermolysis of [TCT]22- yields [TCBT]-. Chemical reduction of 2,4,6-tricyanobenzene, TCB, forms an unstable radical anion that immediately undergoes dimerization at a ring carbon to form [C12H6N6]2-, [TCB]22-, which has a long 1.560 (5) A central C - C bond. Reaction of TCT with tetrathiafulvalene (TTF) forms structurally characterized [TTF][TCT], and in the presence of water, TCT hydrolyzes to 2,4-dicyano-6-hydroxy-s-triazine, DCTOH. In contrast, the reaction of TCT with TMPD forms [TMPD][TCT], which in the presence of water forms structurally characterized [HTMPD]+[DCTO]-.
- Del Sesto, Rico E.,Arif, Atta M.,Novoa, Juan J.,Anusiewicz, Iwona,Skurski, Piotr,Simons, Jack,Dunn, Brian C.,Eyring, Edward M.,Miller, Joel S.
-
-
Read Online
- Synthesis of linear and hyperbranched tetrazine-based polyhetarylene assemblies with high nitrogen content
-
The synthesis of polyhetarylenes containing exclusively s-tetrazine and another nitrogen heterocycle (pyridine or s-triazine) is described. The key step involved the polymerization of a suitable di- or triamidrazone, leading to a linear or hyperbranched dihydrotetrazine-based assembly, respectively. The triazinylenetetrazinylene material stands as one of the most nitrogenated polymers ever described.
- Sagot,Le Roux,Soulivet,Pasquinet,Poullain,Girard,Palmas
-
-
Read Online