Mondal Kartik Chandra, Samuel Prinson P, Roesky Herbert W, Niepötter Benedikt, Herbst-Irmer Regine, Stalke Dietmar, Ehret Fabian, Kaim Wolfgang, Maity Bholanath, Koley Debasis
Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077 Göttingen (Germany), Fax: (+49) 551-39-33373.
Chemistry. 2014 Jul 21;20(30):9240-5. doi: 10.1002/chem.201400393. Epub 2014 Mar 24.
The trichlorosilylcarbene monoradical (Cy-cAAC ·)SiCl3 (1) was directly converted to (Cy-cAAC ·)SiPh3 (2) by substitution of the three chlorine atoms with phenyl groups without affecting the radical center adjacent to the silicon atom. In addition to the structure determination, compound 2 was studied by EPR spectroscopy and DFT calculations. The three hyperfine lines in the EPR spectrum of 2 are due to the coupling with (14)N nucleus. Functionalized 1,4-quinodimethane Me2-cAAC=C6H4=CPh2 (7) was isolated, whereas carbon analogue of radical 2 was targeted. Cyclic voltammogram of 7 indicated that a stable radical-anion 7 ·-, as well as a radical-cation 7 ·+, can be prepared. Theoretical calculations showed that one-electron ionization energy and electron affinity of 7 are 5.1 and 0.7 eV mol(-1), respectively.
三氯甲硅烷基卡宾单自由基（Cy-cAAC·）SiCl₃（1）通过用苯基取代三个氯原子直接转化为（Cy-cAAC·）SiPh₃（2），而不影响与硅原子相邻的自由基中心。除了结构测定外，还通过电子顺磁共振光谱（EPR）和密度泛函理论（DFT）计算对化合物2进行了研究。2的EPR光谱中的三条超精细线是由于与¹⁴N核的耦合。分离出了功能化的1,4-醌二甲烷Me₂-cAAC=C₆H₄=CPh₂（7），而自由基2的碳类似物是目标产物。7的循环伏安图表明，可以制备稳定的自由基阴离子7⁻·和自由基阳离子7⁺·。理论计算表明，7的单电子电离能和电子亲和能分别为5.1和0.7 eV mol⁻¹。
