Structural and Spectroscopic Characterization of an Electrophilic Iron Nitrido Complex

We have isolated and structurally characterized a terminal iron nitrido complex supported by a bulky tris(carbene)borate ligand. The electronic structure of this complex reveals that the a1 LUMO (formerly Fe(d z 2 )) is strongly stabilized by reduced antibonding interactions with the carbene σ-donor...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2008-08, Vol.130 (32), p.10515-10517
Main Authors: Scepaniak, Jeremiah J, Fulton, Meita D, Bontchev, Ranko P, Duesler, Eileen N, Kirk, Martin L, Smith, Jeremy M
Format: Article
Language:English
Subjects:
Boron Compounds - chemical synthesis
Boron Compounds - chemistry
Crystallography, X-Ray
Ferrous Compounds - chemical synthesis
Ferrous Compounds - chemistry
Iron - chemistry
Ligands
Molecular Structure
Spectrum Analysis
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Summary:We have isolated and structurally characterized a terminal iron nitrido complex supported by a bulky tris(carbene)borate ligand. The electronic structure of this complex reveals that the a1 LUMO (formerly Fe(d z 2 )) is strongly stabilized by reduced antibonding interactions with the carbene σ-donor ligands and configurational mixing (hybridization) with higher lying Fe 4s and 4p atomic orbitals. This unusual bonding interaction results in a low-lying Fe nitrido acceptor orbital (LUMO) that possesses electrophilic character. Reaction with PPh3 results in nitrogen atom transfer to the phosphine, supporting a reaction mechanism involving nucleophilic attack of the triphenylphosphine HOMO at the electrophilic LUMO of the iron nitrido complex.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja8027372