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Counterion Dependence of Dinitrogen Activation and Functionalization by a Diniobium Hydride Anion
Author(s) -
Suzuki Shoi,
Ishida Yutaka,
Kameo Hajime,
Sakaki Shigeyoshi,
Kawaguchi Hiroyuki
Publication year - 2020
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.202006039
Subject(s) - chemistry , hydride , counterion , alkali metal , medicinal chemistry , derivative (finance) , imide , inorganic chemistry , reactivity (psychology) , surface modification , cleavage (geology) , bond cleavage , potassium , silylation , lithium (medication) , metal , stereochemistry , polymer chemistry , ion , organic chemistry , catalysis , medicine , alternative medicine , pathology , endocrinology , fracture (geology) , financial economics , economics , geotechnical engineering , engineering
We report the synthesis of anionic diniobium hydride complexes with a series of alkali metal cations (Li + , Na + , and K + ) and the counterion dependence of their reactivity with N 2 . Exposure of these complexes to N 2 initially produces the corresponding side‐on end‐on N 2 complexes, the fate of which depends on the nature of countercations. The lithium derivative undergoes stepwise migratory insertion of the hydride ligands onto the aryloxide units, yielding the end‐on bridging N 2 complex. For the potassium derivative, the N−N bond cleavage takes place along with H 2 elimination to form the nitride complex. Treatment of the side‐on end‐on N 2 complex with Me 3 SiCl results in silylation of the terminal N atom and subsequent N−N bond cleavage along with H 2 elimination, giving the nitride‐imide‐bridged diniobium complex.