%0 Journal Article %1 Gloeckle.2001 %A Gloeckle, Markus %A Huebler, Klaus %A Kuemmerer, Hans-Juergen %A Denninger, Gert %A Kaim, Wolfgang. %D 2001 %J Inorganic Chemistry %K complex complex;ESR copper dinuclear prepn pyrimidyltetrazine structure structure;crystal %N 10 %P 2263--2269 %R 10.1021/ic001228q %T Dicopper(I) Complexes with Reduced States of 3,6-Bis(2'-pyrimidyl)-1,2,4,5-tetrazine: Crystal Structures and Spectroscopic Properties of the Free Ligand, a Radical Species, and a Complex of the 1,4-Dihydro Form %V 40 %X (μ-Bmtz.bul.-)Cu(PPh3)22(BF4) (1) and (μ-H2bmtz)Cu(PPh3)22(BF4)2 (2) (bmtz = 3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine and H2bmtz = 1,4-dihydro-3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine) were obtained as stable materials that could be crystd. for structure detn. 1·2CH2Cl2: C84H70BCl4Cu2F4N8P4; monoclinic, space group C2/c; a 26.215(7), b 22.122(6), c 18.114(5) \AA, b 133.51(1)°; Z = 4. 2·CH2Cl2: C83H70B2Cl2Cu2F8N8P4; triclinic, space group P1̅; a 10.948(2), b 12.067(2), c 30.287(6) \AA, a 93.82(3), b 94.46(3), g 101.60(3)°; Z = 2. Bmtz itself was also structurally characterized (C10H6N8; monoclinic, space group P21/c; a 3.8234(8), b 10.147(2), c 13.195(3) \AA, b 94.92(3)°; Z = 2). Whereas the radical complex ion contains a planar tetrazine ring in the center, the 1,4-dihydrotetrazine heterocycle in the corresponding complex of H2bmtz is considerably folded. Both systems exhibit slight twists between the tetrazine and the pyrimidine rings. The intra-tetrazine distances are characteristically affected by the electron transfer, as is also evident from a comparison with the new structure of free bmtz; the bonding to Cu(I) changes accordingly. Spectroscopy including X- and W-band EPR of the radical species confirms that the electron addn. is mainly to the tetrazine ring. on SciFinder(R)

@article{Gloeckle.2001, abstract = {{(μ-Bmtz.bul.-)[Cu(PPh3)2]2}(BF4) (1) and {(μ-H2bmtz)[Cu(PPh3)2]2}(BF4)2 (2) (bmtz = 3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine and H2bmtz = 1,4-dihydro-3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine) were obtained as stable materials that could be crystd. for structure detn. 1·2CH2Cl2: C84H70BCl4Cu2F4N8P4; monoclinic, space group C2/c; a 26.215(7), b 22.122(6), c 18.114(5) {\AA}, \textgreek{b} 133.51(1)°; Z = 4. 2·CH2Cl2: C83H70B2Cl2Cu2F8N8P4; triclinic, space group P1̅; a 10.948(2), b 12.067(2), c 30.287(6) {\AA}, \textgreek{a} 93.82(3), \textgreek{b} 94.46(3), \textgreek{g} 101.60(3)°; Z = 2. Bmtz itself was also structurally characterized (C10H6N8; monoclinic, space group P21/c; a 3.8234(8), b 10.147(2), c 13.195(3) {\AA}, \textgreek{b} 94.92(3)°; Z = 2). Whereas the radical complex ion contains a planar tetrazine ring in the center, the 1,4-dihydrotetrazine heterocycle in the corresponding complex of H2bmtz is considerably folded. Both systems exhibit slight twists between the tetrazine and the pyrimidine rings. The intra-tetrazine distances are characteristically affected by the electron transfer, as is also evident from a comparison with the new structure of free bmtz; the bonding to Cu(I) changes accordingly. Spectroscopy including X- and W-band EPR of the radical species confirms that the electron addn. is mainly to the tetrazine ring. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Gloeckle, Markus and Huebler, Klaus and Kuemmerer, Hans-Juergen and Denninger, Gert and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2ec9cab412bf54dc66b3fa4cab2f292e9/huebleriac}, doi = {10.1021/ic001228q}, interhash = {97e0a12776742de5774d96ff4f0d483f}, intrahash = {ec9cab412bf54dc66b3fa4cab2f292e9}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {complex complex;ESR copper dinuclear prepn pyrimidyltetrazine structure structure;crystal}, number = 10, pages = {2263--2269}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Dicopper(I) Complexes with Reduced States of 3,6-Bis(2'-pyrimidyl)-1,2,4,5-tetrazine: Crystal Structures and Spectroscopic Properties of the Free Ligand, a Radical Species, and a Complex of the 1,4-Dihydro Form}, volume = 40, year = 2001 }