An Isolable Diphosphene Radical Cation Stabilized by Three‐Center Three‐Electron π‐Bonding with Chromium: End‐On versus Side‐On Coordination | Zendy

Wang Wenqing | Zendy; Xu CongQiao | Zendy; Fang Yong | Zendy; Zhao Yue | Zendy; Li Jun | Zendy; Wang Xinping | Zendy

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An Isolable Diphosphene Radical Cation Stabilized by Three‐Center Three‐Electron π‐Bonding with Chromium: End‐On versus Side‐On Coordination

Author(s) -

Wang Wenqing,

Xu CongQiao,

Fang Yong,

Zhao Yue,

Li Jun,

Wang Xinping

Publication year - 2018

Publication title -

angewandte chemie international edition

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 5.831

H-Index - 550

eISSN - 1521-3773

pISSN - 1433-7851

DOI - 10.1002/anie.201805115

Subject(s) - electron paramagnetic resonance , unpaired electron , delocalized electron , chemistry , crystallography , atom (system on chip) , center (category theory) , chromium , radical ion , ligand (biochemistry) , radical , spectroscopy , photochemistry , nuclear magnetic resonance , ion , physics , organic chemistry , biochemistry , receptor , quantum mechanics , computer science , embedded system

Two salts ( 2 and 4 ) containing the radical cations of complexed diphosphenes have been isolated and characterized by electron paramagnetic resonance (EPR) spectroscopy, IR spectroscopy, and single‐crystal X‐ray diffraction. The P−P bond is coordinated to the Cr center either in an end‐on (in 2 ) or a side‐on (in 4 ) fashion. The spin density of the radical is delocalized over the Cr atom and the two P atoms in 2 whereas the unpaired electron is mainly localized on the Cr atom in 4 . This work provides the first example of a complexed diphosphene radical ( 2 ) featuring novel three‐center three‐electron (3c‐3e) π‐bonding in the Cr‐P‐P unit, and the first example of a 17 e Cr radical with a side‐on π‐bonded ligand ( 4 ).

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