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Selective Nitrogen‐Atom Transfer Driven by a Highly Efficient Intersystem Crossing in the [CeON] + /CH 4 System
Author(s) -
Zhou Shaodong,
Sun Xiaoyan,
Yue Lei,
Guo Cheng,
Schlangen Maria,
Schwarz Helmut
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.201809583
Subject(s) - intersystem crossing , chemistry , methane , molecule , ion , atom (system on chip) , nitrogen , photochemistry , nitrogen atom , photodissociation , atomic physics , excited state , physics , organic chemistry , computer science , singlet state , embedded system , group (periodic table)
The thermal gas‐phase reactions of [CeON] + with methane have been explored by FT‐ICR mass spectrometry and high‐level quantum‐chemical calculations. Nitrogen‐atom transfer from the cluster ion to methane was observed as the only reaction channel. Based on computational work, the neutral molecule formed corresponds to either CH 2 NH 2 or CH 3 NH. In addition to a rather weak OCe + −N bond, this reaction benefits from a highly efficient intersystem crossing. Mechanistic aspects and the associated electronic origins are discussed, and a detailed comparison of [CeON] + , [CeO] + , [CeN] + , [CeO 2 ] + , and atomic N in their reactions with CH 4 is given.