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Complexes with Nitrogen‐Centered Radical Ligands: Classification, Spectroscopic Features, Reactivity, and Catalytic Applications
Author(s) -
Suarez Alma I. Olivos,
Lyaskovskyy Volodymyr,
Reek Joost N. H.,
van der Vlugt Jarl Ivar,
de Bruin Bas
Publication year - 2013
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.201301487
Subject(s) - reactivity (psychology) , nitrene , chemistry , catalysis , photochemistry , nitrogen , ligand (biochemistry) , combinatorial chemistry , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology
The electronic structure, spectroscopic features, and (catalytic) reactivity of complexes with nitrogen‐centered radical ligands are described. Complexes with aminyl ([M( . NR 2 )]), nitrene/imidyl ([M( . NR)]), and nitridyl radical ligands ([M( . N)]) are detectable and sometimes even isolable species, and despite their radical nature frequently reveal selective reactivity patterns towards a variety of organic substrates. A classification system for complexes with nitrogen‐centered radical ligands based on their electronic structure leads to their description as one‐electron‐reduced Fischer‐type systems, one‐electron‐oxidized Schrock‐type systems, or systems with a (nearly) covalent MN π bond. Experimental data relevant for the assignment of the radical locus (i.e. metal or ligand) are discussed, and the application of complexes with nitrogen‐centered radical ligands in the (catalytic) syntheses of nitrogen‐containing organic molecules such as aziridines and amines is demonstrated with recent examples. This Review should contribute to a better understanding of the (catalytic) reactivity of nitrogen‐centered radical ligands and the role they play in tuning the reactivity of coordination compounds.