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Efficient Electronic Structure to Stabilize N 2 ‐Bridged Dinuclear Complexes Intended for N 2 Activation: Iminophosphorane Iron(I) and Cobalt(I)
Author(s) -
WasadaTsutsui Yuko,
Wasada Hiroaki,
Suzuki Tatsuya,
Katayama Akira,
Kajita Yuji,
Inomata Tomohiko,
Ozawa Tomohiro,
Masuda Hideki
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201901131
Subject(s) - chemistry , antibonding molecular orbital , crystallography , atomic orbital , density functional theory , ligand (biochemistry) , catalysis , molecular orbital , spectrochemical series , stereochemistry , computational chemistry , ligand field theory , molecule , electron , ion , biochemistry , physics , receptor , organic chemistry , quantum mechanics
We examined the stability of the N 2 ‐ligated mononuclear and N 2 ‐bridged dinuclear complexes for Fe I and Co I with the tridentate iminophosphorane ligand, which are in potentially deactivated state for catalytic N 2 fixation processes, using density functional theory (DFT) method. The calculated Gibbs free energies of the N 2 binding and N 2 ‐bridge formation reactions show that the N 2 ‐bridged Fe I ‐dinuclear complex is more favorable than the N 2 Fe I ‐mononuclear complex in contrast to the Co I ‐mononuclear complexes, which is only the available complex, even if at –80 °C. The stability of the N 2 ‐bridged dinuclear metal complexes has a close relation to the M–N 2 bond strength ruled by occupation of the pairs of d πu orbitals, in which the ungerade couples of the d π orbitals interact with the occupied π orbitals of N 2 in antibonding manner. For the catalytic activity of Fe I mononuclear complexes, the appropriate order of orbitals to occupy the d πu orbitals is necessary, which is produced by the T‐shaped coordination geometry the ancillary ligands construct.