Title |
Complexes with Nitrogen‐Centered Radical Ligands: Classification, Spectroscopic Features, Reactivity, and Catalytic Applications
|
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Published in |
Angewandte Chemie. International Edition, November 2013
|
DOI | 10.1002/anie.201301487 |
Pubmed ID | |
Authors |
Alma I. Olivos Suarez, Volodymyr Lyaskovskyy, Joost N. H. Reek, Jarl Ivar van der Vlugt, Bas de Bruin |
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 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. |
X Demographics
Geographical breakdown
Country | Count | As % |
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Netherlands | 1 | 33% |
Germany | 1 | 33% |
Unknown | 1 | 33% |
Demographic breakdown
Type | Count | As % |
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Scientists | 2 | 67% |
Members of the public | 1 | 33% |
Mendeley readers
Geographical breakdown
Country | Count | As % |
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Netherlands | 3 | 2% |
Iran, Islamic Republic of | 1 | <1% |
France | 1 | <1% |
Unknown | 133 | 96% |
Demographic breakdown
Readers by professional status | Count | As % |
---|---|---|
Student > Ph. D. Student | 41 | 30% |
Student > Master | 22 | 16% |
Student > Bachelor | 17 | 12% |
Researcher | 13 | 9% |
Professor > Associate Professor | 7 | 5% |
Other | 20 | 14% |
Unknown | 18 | 13% |
Readers by discipline | Count | As % |
---|---|---|
Chemistry | 107 | 78% |
Engineering | 2 | 1% |
Biochemistry, Genetics and Molecular Biology | 1 | <1% |
Agricultural and Biological Sciences | 1 | <1% |
Physics and Astronomy | 1 | <1% |
Other | 5 | 4% |
Unknown | 21 | 15% |