Journal article
Nitrogen Atom Transfer from Iron(IV) Nitrido Complexes: A Dual-Nature Transition State for Atom Transfer
Inorganic chemistry, v 50(19), pp 9508-9517
03 Oct 2011
PMID: 21902179
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
The mechanism of nitrogen atom transfer from four-coordinate tris(carbene)borate iron (IV) nitrido complexes to phosphines and phosphites has been investigated. In the absence of limiting steric effects, the rate of nitrogen atom transfer to phosphines increases with decreasing phosphine sigma-basicity. This trend has been quantified by a Hammett study with para-substituted triarylphosphines, and is contrary to the expectations of an electrophilic nitrido ligand. On the basis of electronic structure calculations, a dual-nature transition state for nitrogen atom transfer is proposed, in which a key interaction involves the transfer of electron density from the nitrido highest occupied molecular orbital (HOMO) to the phosphine lowest unoccupied molecular orbital (LUMO). Compared to analogous atom transfer reactions from a 5d metal, these results show how the electronic plasticity of a 3d metal results in rapid atom transfer from pseudotetrahedral late metal complexes.
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Details
- Title
- Nitrogen Atom Transfer from Iron(IV) Nitrido Complexes: A Dual-Nature Transition State for Atom Transfer
- Creators
- Jeremiah J. Scepaniak - New Mexico State UniversityCharles G. Margarit - New Mexico State UniversityJeremy N. Harvey - University of BristolJeremy M. Smith - New Mexico State University
- Publication Details
- Inorganic chemistry, v 50(19), pp 9508-9517
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 10
- Grant note
- Dreyfus Foundation DE-FG02-08ER15996 / DOE-BES; United States Department of Energy (DOE)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000295115000039
- Scopus ID
- 2-s2.0-80053305400
- Other Identifier
- 991020902862704721
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- Collaboration types
- Domestic collaboration
- International collaboration
- Web of Science research areas
- Chemistry, Inorganic & Nuclear