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Complexes with Nitrogen-Centered Radical Ligands: Classification, Spectroscopic Features, Reactivity, and Catalytic Applications.
- Source :
-
Angewandte Chemie International Edition . Nov2013, Vol. 52 Issue 48, p12510-12529. 20p. - Publication Year :
- 2013
-
Abstract
- The electronic structure, spectroscopic features, and (catalytic) reactivity of complexes with nitrogen-centered radical ligands are described. Complexes with aminyl ([M(.NR2)]), 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. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14337851
- Volume :
- 52
- Issue :
- 48
- Database :
- Academic Search Index
- Journal :
- Angewandte Chemie International Edition
- Publication Type :
- Academic Journal
- Accession number :
- 92016622
- Full Text :
- https://doi.org/10.1002/anie.201301487