Theoretical Study on Electronic Structure of (CNC)Fe_2N2 and Its N2 Elimination Mechanism

被引:5
作者
Zhang, Xiang [1 ]
机构
[1] Shanxi Normal Uniovsers, Sch Chem & Mat Sci, Linfen 041004, Peoples R China
关键词
density function theory; N2 elimination mechanism; nonadiabatic process; WAVE-PACKET; DINITROGEN COMPLEXES; CHEMICAL-REACTIONS; DYNAMICS; ENERGY; IRON; PHOTODISSOCIATION; PROTONATION; MOLYBDENUM; RUTHENIUM;
D O I
10.1002/qua.22382
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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 pi* orbitals (LUF(4)O and LUF(4)O-1) of apical N3-N4 is 0.188 while that of basal N1-N2 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 Fe-N3 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)Fe-N-2. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 110: 1880-1889, 2010
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页码:1880 / 1889
页数:10
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