Dinitrogen Chemistry from Trigonally Coordinated Iron and Cobalt Platforms
- Creators
- Betley, Theodore A.
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Peters, Jonas C.
Abstract
This report establishes that trigonally coordinated "[PhBP^(iPr)_(3)]M" platforms (M = Fe, Co) will support both π-acidic (N_2) and π-basic (NR) ligands at a fourth binding site. The N_2 complexes of iron that are described are the first thoroughly characterized examples to exhibit a 4-coordinate geometry. Methylation of monomeric {Fe^(0)(N_(2))-} and {Co^(0)(N_(2))-} species successfully derivatizes the β-N atom of the coordinated N_(2) ligand and affords the diazenido products {Fe^(II)(N_(2)Me)} and {CoII(N2Me)}, respectively. One-electron oxidation of the mononuclear M^(0)(N_(2))- species produces dinuclear and synthetically versatile M^(I)(N_(2))M^(I) complexes. These latter species provide clean access to the chemistry of the "[PhBP^(iPr)_(3)]M^(I)" subunit. For example, addition of RN_(3) to M^(I)(N_(2))M^(I) results in oxidative nitrene transfer to generate [PhBP^(iPr)_(3)]M_(≡)NR with concomitant N_(2) release.
Additional Information
© 2003 American Chemical Society. Received June 14, 2003. This work was supported by a DOE PECASE award. T.A.B. is grateful for a Department of Defense graduate research fellowship.Attached Files
Supplemental Material - ja036687fsi20030714_062420.pd
Supplemental Material - ja036687fsi20030714_062420.pdf
Supplemental Material - ja036687fsi20030714_062459.ci
Supplemental Material - ja036687fsi20030714_062459.cif
Files
Additional details
- Eprint ID
- 47433
- DOI
- 10.1021/ja036687f
- Resolver ID
- CaltechAUTHORS:20140723-132701006
- Department of Energy (DOE) PECASE award
- Created
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2014-07-23Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field