title: Structural and spectroscopic characterization of an electrophilic iron nitrido complex.
abstract: 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(dz2)) is strongly stabilized by reduced antibonding interactions with the carbene sigma-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.
authors.affiliation: Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces, New Mexico 88003, USA.
authors.forename: Jeremiah J
authors.initials: JJ
authors.lastname: Scepaniak
authors.forename: Meita D
authors.initials: MD
authors.lastname: Fulton
authors.forename: Ranko P
authors.initials: RP
authors.lastname: Bontchev
authors.forename: Eileen N
authors.initials: EN
authors.lastname: Duesler
authors.forename: Martin L
authors.initials: ML
authors.lastname: Kirk
authors.forename: Jeremy M
authors.initials: JM
authors.lastname: Smith
mesh_terms: D001896:Boron Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D013057:Spectrum Analysis
chemical_list: D001896:Boron Compounds; D005296:Ferrous Compounds; D008024:Ligands; D007501:Iron