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Published September 10, 2003 | Supplemental Material
Journal Article Open

Dinitrogen Chemistry from Trigonally Coordinated Iron and Cobalt Platforms

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.

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Supplemental Material - ja036687fsi20030714_062420.pdf

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Supplemental Material - ja036687fsi20030714_062459.cif

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