The Tetracyanopyrazinide Dimer Dianion, [TCNP][sub2][sup2-] 2-Electron 8-Center Bonding.
The reaction of Cr(CH) and 1,2,4,5-tetracyanopyrazine (TCNP) forms [Cr(CH)][TCNP], and TCNP is reduced and forms the eclipsed π[TCNP] dimer. Diamagnetic [TCNP] has an intradimer separation of 3.14(2) Å. The intradimer C⋯C and N⋯N separations are 3.29(2) and 3.42(2) Å, respectively, and increase with...
| Publicado en: | Journal of the American Chemical Society Vol. 131; no. 25; pp. 9070 - 9076 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
7/1/2009
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=43417419&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 43417419 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 7/1/2009 vid: 131 iid: 25 pid: 997 pub: American Chemical Society artinfo: ui: 43417419 10.1021/ja902790q ppf: 9070 ppct: 6 formats: tig: atl: The Tetracyanopyrazinide Dimer Dianion, [TCNP][sub2][sup2-] 2-Electron 8-Center Bonding. aug: au: Novoa, Juan J. Stephens, Peter W. Weerasekare, Mahika Shum, William W. Miller, Joel S. affil: Department of Physics & Astronomy, Stony Brook University, Stony Brook, New York 11794-3800 Departament de Química Física and IQTCUB, Facultat de Química, Universitat de Barcelona, Au. Diagonal 647, 08028-Barcelona, Spain Department of Chemistry, 315 5. 1400 E. RM 2124, University of Utah, Salt Lake City, Utah 84112-0850 su: Dimers Chemical reactions Diamagnetism Superconductivity Diffraction patterns Atomic structure sug: subj: Dimers Chemical reactions Diamagnetism Superconductivity Diffraction patterns Atomic structure ab: The reaction of Cr(CH) and 1,2,4,5-tetracyanopyrazine (TCNP) forms [Cr(CH)][TCNP], and TCNP is reduced and forms the eclipsed π[TCNP] dimer. Diamagnetic [TCNP] has an intradimer separation of 3.14(2) Å. The intradimer C⋯C and N⋯N separations are 3.29(2) and 3.42(2) Å, respectively, and increase with the distance from the center Of the molecule, due to nitriles bending away from the plane of themolecule by 5 ± 1°. [TCNP] is best described by an atoms-in-molecules analysis as having a 2e/8c C-C bond involving the four C atoms from each six-member ring. The results of B3LYP/6-31 +G(d)- computed interactions indicate that the [TCNP]⋯[TCNP] interactions in an isolated [TCNP] are repulsive by 58.9 kcal/rnol, and that the stability of [TCNP] primarily originates from [TCNP]⋯cation electrostatic interactions, whose sum (-209.8 kcal/mol) exceeds the sum of the repulsive [TCNP]⋯[TCNP] and cation⋯cation interactions (140.3 kcal/mol). pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2009 holdings: @attributes: islocal: N |
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