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

被引:34
作者
Del Sesto, RE
Arif, AM
Novoa, JJ
Anusiewicz, I
Skurski, P
Simons, J
Dunn, BC
Eyring, EM
Miller, JS
机构
[1] Univ Utah, Dept Chem, Salt Lake City, UT 84112 USA
[2] Univ Barcelona, Dept Phys Chem, E-08028 Barcelona, Spain
[3] Univ Gdansk, Inst Chem, PL-80952 Gdansk, Poland
关键词
D O I
10.1021/jo025833h
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
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 [Cl2N12](2-), [TCT](2)(2-), characterized by a long 1.570 (4) Angstrom central C-C bond. [TCT](2)(2-) can decompose into the radical anion of 4,4',6;6'-tetracyano-2,2'-bitriazine, [TCBT](.-), the one-electron reduced form of planar (D-2h) TCBT, which is also structurally characterized as the [TMPD] [TCBT] charge-transfer complex (TMPD = N,NN',N'-tetramethyl-p-phenylenediamine) with a 1.492 (2) Angstrom central sp(2)-sp(2) C-C bond. Although crystals could not be obtained for the radical anion [TCBT](.-), the electrochemistry (Edegrees = +0.03 V), EPR (g = 2.003, (2)A(14N) = 3.347 G, and (4)A(14N) = 0.765 G and a line width of 0.24 G), and theoretical calculations support the formation of [TCBT](.-). In addition, thermolysis of [TCT](2)(2-) 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](2)(2-), which has a long 1.560 (5) Angstrom 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](-).
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页码:3367 / 3379
页数:13
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