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Synthesis and properties of hypervalent electron-rich pentacoordinate nitrogen compounds.


ABSTRACT: Isolation and structural characterization of hypervalent electron-rich pentacoordinate nitrogen species have not been achieved despite continuous attempts for over a century. Herein we report the first synthesis and isolation of air stable hypervalent electron-rich pentacoordinate nitrogen cationic radical (11-N-5) species from oxidation of their corresponding neutral (12-N-5) species. In the cationic radical species, the nitrogen centers adopt a trigonal bipyramidal geometry featuring a 3-center-5-electron hypervalent attractive interaction. The combination of single crystal X-ray diffraction analysis and computational studies revealed weak N-O interactions between the central nitrogen cation and oxygen atoms. This successful design strategy and isolation of air-stable pentacoordinate hypervalent nitrogen species allow further investigations on reactivity and properties resulting from these unusually weakly coordinating interactions in nitrogen compounds.

SUBMITTER: Yan C 

PROVIDER: S-EPMC8159240 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

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Synthesis and properties of hypervalent electron-rich pentacoordinate nitrogen compounds.

Yan Chenting C   Takeshita Masato M   Nakatsuji Jun-Ya JY   Kurosaki Akihiro A   Sato Kaoko K   Shang Rong R   Nakamoto Masaaki M   Yamamoto Yohsuke Y   Adachi Yohei Y   Furukawa Ko K   Kishi Ryohei R   Nakano Masayoshi M  

Chemical science 20200422 19


Isolation and structural characterization of hypervalent electron-rich pentacoordinate nitrogen species have not been achieved despite continuous attempts for over a century. Herein we report the first synthesis and isolation of air stable hypervalent electron-rich pentacoordinate nitrogen cationic radical (<b>11-N-5</b>) species from oxidation of their corresponding neutral (<b>12-N-5</b>) species. In the cationic radical species, the nitrogen centers adopt a trigonal bipyramidal geometry featu  ...[more]

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