Isolable cyclic radical cations of heavy main-group elements

Haiyan Cui; Dengmengfei Xiao; Li Zhang; Huapeng Ruan; Yong Fang; Yue Zhao; Gengwen Tan; Lili Zhao; Gernot Frenking; Matthias Driess; Xinping Wang

doi:10.1039/C9CC09582A

Isolable cyclic radical cations of heavy main-group elements†

Haiyan Cui,^ab Dengmengfei Xiao,^c Li Zhang,^b Huapeng Ruan,^b Yong Fang,^b Yue Zhao,

^b Gengwen Tan,

*^b Lili Zhao,

*^c Gernot Frenking,

*^cd Matthias Driess

^e and Xinping Wang

*^b

Author affiliations

* Corresponding authors

^a Jiangsu Key Laboratory of Pesticide Science, College of Sciences, Nanjing Agricultural University, Nanjing 210095, China

^b State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
E-mail: gengwentan@nju.edu.cn, xpwang@nju.edu.cn

^c Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing 211816, China
E-mail: ias_llzhao@njtech.edu.cn, frenking@chemie.uni-marburg.de

^d Fachbereich Chemie, Philipps-Universität Marburg Hans-Meerwein-Strasse 4, 35032 Marburg, Germany

^e Department of Chemistry, Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany

Abstract

One-electron oxidation of 1,3-digerma-2,4-dipnictacyclobutadiene [L^HGeE]₂ (L^H = CH[CHNDipp]₂, dipp = 2,6-ⁱPr₂C₆H₃; 1: E = P; 2: E = As) with Ag[Al(OR_F)₄] (R_F = C(CF₃)₃) afforded the stable radical cation salts 1˙⁺·[Al(OR_F)₄]⁻ and 2˙⁺·[Al(OR_F)₄]⁻, respectively. The radical cation salts have been fully characterized, in conjunction with theoretical calculations. The EPR spectroscopic studies and DFT calculations reveal that the spin density mainly resides at the heavy pnictogen atoms, rather than delocalizes over the Ge₂E₂ ring. They represent the first structurally characterized cyclic radical species composed of both heavy group 14 and 15 elements.

Chemical Communications

Isolable cyclic radical cations of heavy main-group elements†

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Isolable cyclic radical cations of heavy main-group elements

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