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Tricoordinate Nontrigonal Pnictogen‐Centered Radical Anions: Isolation, Characterization, and Reactivity
Author(s) -
Mondal Manas Kumar,
Zhang Li,
Feng Zhongtao,
Tang Shuxuan,
Feng Rui,
Zhao Yue,
Tan Gengwen,
Ruan Huapeng,
Wang Xinping
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201910139
Subject(s) - pnictogen , reactivity (psychology) , chemistry , radical , crystallography , electron paramagnetic resonance , group (periodic table) , main group element , ligand (biochemistry) , atomic orbital , amide , characterization (materials science) , electron , materials science , nuclear magnetic resonance , nanotechnology , transition metal , physics , organic chemistry , condensed matter physics , medicine , alternative medicine , superconductivity , pathology , quantum mechanics , biochemistry , receptor , catalysis
The search for main‐group element‐based radicals is one of the main research topics in contemporary chemistry because of their fascinating chemical and physical properties. The Group 15 element‐centered radicals mainly feature a V‐shaped two coordinate structure, with a couple of radical cations featuring trigonal tricoordinated geometry. Now, nontrigonal compounds R 3 E (E=P, As, Sb) were successfully synthesized by introducing a new rigid tris‐amide ligand. The selective one‐electron reduction of R 3 E afforded the first stable tricoordinate pnictogen‐centered radical anion salts; the pnictogen atoms retain planar T‐shaped structures. EPR spectroscopy and calculations reveal that the spin density mainly resides at the p orbitals of the pnictogen atoms, which is perpendicular to the N 3 E planes.