Chem. J. Chinese Universities ›› 2012, Vol. 33 ›› Issue (08): 1799.doi: 10.3969/j.issn.0251-0790.2012.08.030

• Physical Chemistry • Previous Articles     Next Articles

Theoretical Design of a New N-Heterocyclic Carbene Complex Based on Non-heme Iron Complex [Fe(O)(N4Py)]2+

WANG Yi1, ZHANG Peng2, YANG Kun3, HOU Ying-Min1   

  1. 1. School of Biological Engineering, Dalian Polytechnic University, Dalian 116034, China;
    2. School of Mechanical Engineering and Automation, Dalian Polytechnic University, Dalian 116034, China;
    3. Department of Physics, Dalian Maritime University, Dalian 116026, China
  • Received:2011-11-30 Online:2012-08-10 Published:2012-08-10

Abstract:

Based on non-heme iron complex [Fe(O)(N4Py)]2+, a new designed iron-carbene complex [Fe(O)(N4Py)]2+ was theoretically designed. The geometric and electronic structures of [Fe(O)(N4Py)]2+ were studied via density functional theory and B3LYP method, and the [Fe(O)(N4Py)]2+ catalytic properties versus cyclohexane were investigated. The calculation results show that the energy of the quintet spin state of [Fe(O)(N4Py)]2+ is ca. 4.8 kJ/mol higher than that of the triplet ground state, suggesting that the quintet spin state can hardly participate in the reaction. The N-heterocyclic carbene (NHC) equatorial ligand was found to have stronger σ-donating and greater steric hindrance than N4Py ligand, indicating that the complex [Fe(O)(N4Py)]2+ is more stable than [Fe(O)(N4Py)]2+ complex. Moreover, on the triplet spin surface, the energy barrier of [Fe(O)(N4Py)]2+ has higher activation energy than that of [Fe(O)(N4Py)]2+ by 2.0 kJ/mol via a single-state reactivity pattern, implying that [Fe(O)(N4Py)]2+ complex is more reactive than [Fe(O)(N4Py)]2+ complex.

Key words: Non-heme, N-Heterocyclic carbene, Density functional theory, Orbital coefficient, Reaction mechanism

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