Murakami Fumiki, Sasaki Shigeru, Yoshifuji Masaaki
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba, Sendai 980-8578, Japan.
J Am Chem Soc. 2005 Jun 29;127(25):8926-7. doi: 10.1021/ja052271l.
Phosphaquinomethane and phosphathienoquinomethanes sterically protected by Mes* (Mes* = 2,4,6-tri-tert-butylphenyl) were synthesized by 1,6-dehydration of the corresponding 4-phosphinoaryl carbinols. Structural similarities to the conventional quinoid compounds were revealed by 1H, 13C, and 31P NMR study and further confirmed by X-ray crystallography of the phosphathienoquinomethane. The corresponding anion radicals were generated by reduction with sodium, and considerable delocalization of an unpaired electron was demonstrated by EPR.
通过相应的4-膦基芳基甲醇的1,6-脱水反应合成了由Mes*（Mes* = 2,4,6-三叔丁基苯基）空间保护的磷喹甲烷和磷噻吩喹甲烷。通过1H、13C和31P NMR研究揭示了与传统醌类化合物的结构相似性，并通过磷噻吩喹甲烷的X射线晶体学进一步证实。通过用钠还原产生相应的阴离子自由基，EPR证明了未成对电子的显著离域。
