Ligand Tailoring Toward an Air-Stable Iron(V) Nitrido Complex.
J Am Chem Soc
; 143(3): 1458-1465, 2021 Jan 27.
Article
em En
| MEDLINE
| ID: mdl-33430587
ABSTRACT
A new supporting ligand, tris-[2-(3-mesityl-imidazol-2-ylidene)methyl]amine (TIMMNMes), was developed and utilized to isolate an air-stable iron(V) complex bearing a terminal nitrido ligand, which was synthesized by one-electron oxidation from the iron(IV) precursor. Single-crystal X-ray diffraction analyses of both complexes reveal that the metal-centered oxidation is escorted by iron nitride (Fe≡N) bond elongation, which in turn is accompanied by the accommodation of the high-valence iron center closer to the equatorial plane of a trigonal bipyramid. This contrasts with the previous observation of the only other literature-known Fe(IV)≡N/Fe(V)≡N redox pair, namely, [PhB(tBuIm)3FeN]0/+. On the basis of 57Fe Mössbauer, EPR, and UV/vis electronic absorption spectroscopy as well as quantum chemical calculations, we identified the lesser degree of pyramidalization around the iron atom, the Jahn-Teller distortion, and the resulting nature of the SOMO to be the decisive factors at play.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Tipo de estudo:
Prognostic_studies
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2021
Tipo de documento:
Article
País de afiliação:
Alemanha