Premium
High‐Spin Iron(I) and Iron(0) Dinitrogen Complexes Supported by N‐Heterocyclic Carbene Ligands
Author(s) -
Ouyang Zhenwu,
Cheng Jun,
Li Lingling,
Bao Xiaoli,
Deng Liang
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201603390
Subject(s) - carbene , chemistry , spin (aerodynamics) , medicinal chemistry , polymer chemistry , catalysis , organic chemistry , physics , thermodynamics
The use of 1,3‐dicyclohexylimidazol‐2‐ylidene (ICy) as ligand has enabled the preparation of the high‐spin tetrahedral iron(I)‐ and iron(0)–N 2 complexes, namely [(ICy) 3 Fe(N 2 )][BPh 4 ] ( 1 ) and [(ICy) 3 Fe(N 2 )] ( 2 ), the electronic structures of which have been established by various spectroscopic characterization and DFT calculations. The frequency of the N–N stretching resonance of the iron(0)–N 2 complex is the lowest among the reported terminal N 2 complexes of iron, signifying the beneficial roles of strongly σ‐donating ligands in combination with the high‐spin low‐valent iron center in promoting N 2 ‐activation. The iron(0)–N 2 complex can convert reversibly to the low‐spin iron(II)‐N 2 hydride complex [(ICy) 2 (ICy′)Fe(N 2 )(H)] ( 4 ).