Electronic Spectra of the Tetraphenylcyclobutadienecyclopentadienylnickel(II) Cation and Radical
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- 作者：Peter R. Craig ; Zdeněk Havlas ; Marianela Trujillo ; Pawel Rempala ; James P. Kirby ; John R. Miller ; Bruce C. Noll ; Josef Michl
- 刊名：Journal of Physical Chemistry A
- 出版年：2016
- 出版时间：May 26, 2016
- 年：2016
- 卷：120
- 期：20
- 页码：3456-3462
- 全文大小：391K
- 年卷期：0
- ISSN：1520-5215
文摘
Properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF<sub>4sub><sup>–sup> anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical, whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ∼0.1 V upon going from 1 to 1a. Unsuccessful attempts to prepare several other aryl substituted derivatives of 1 by the classical synthetic route are described in the ss="ref" href="#notes-1">Supporting Information.