Premium
Theoretical study on electronic structure of (CNC)Fe_2N 2 and its N 2 elimination mechanism
Author(s) -
Zhang Xiang
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22382
Subject(s) - singlet state , chemistry , density functional theory , atomic orbital , spin states , crystallography , ground state , electronic structure , molecular orbital , spin (aerodynamics) , atomic physics , computational chemistry , molecule , physics , thermodynamics , quantum mechanics , inorganic chemistry , excited state , organic chemistry , electron
The density function theory (DFT) is to elucidate the electronic structure of bis(dinitrogen) Fe(0) complex, (CNC)Fe_2N 2 , and its N 2 elimination mechanism. (CNC)Fe_2N 2 has a low‐spin singlet ( S = 0) ground state with a distorted square pyramidal structure. Fragment orbital interaction analysis yields total occupancy of π* orbitals (LUF (4) O and LUF (4) O−1) of apical N3N4 is 0.188 while that of basal N1N2 is 0.187 in S0 (CNC)Fe_2N 2 , suggesting nearly the same activation extent for both basal and apical N 2 ligands. The lowest‐lying triplet state T 1 (3‐A′) has a repulsive potential energy surface along the FeN3 bong length by PBE functional, while a minimum on T 2 state (3‐A″) with higher energy is found by B3LYP functional. The nonadiabatic N 2 elimination mechanism of (CNC)Fe_2N 2 involves an S 0 ‐T 1 states crossing, which lowers the activation energy to 9.7 kcal/mol and produces high‐spin intermediate (CNC)FeN 2 . © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010