- Complexes with Nitrogen-Centered Radical Ligands: Classification, Spectroscopic Features, Reactivity, and Catalytic Applications
- Angewandte Chemie, International Edition
- Volume | Issue number
- 52 | 48
- Pages (from-to)
- Document type
- Faculty of Science (FNWI)
- Van 't Hoff Institute for Molecular Sciences (HIMS)
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 M.....N 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.
- go to publisher's site
If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library, or send a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible.