Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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A Molecular Orbital Study of the Electronic Structure and the Ring Inversion Process in$Cp_2TiS_3$ Complex

  • Sung Kwon Kang (Department of Chemistry, Chungnam National University) ;
  • Byeong Gak Ahn (Department of Chemistry, Chungnam National University)
  • Published : 1994.08.20
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Abstract

Ab initio and extended Huckel calculations have been applied to discuss the electronic structure, ring inversion barrier, and geometry of the $Cp_2TiS_3$ compound. The deformation of four membered ring in the planar geometry is originated from a second-order Jahn-Teller distortion due to the small energy gap between HOMO and LUMO on the basis of extended Huckel calculations. The puckered $C_s$ geometry is stabilized by the interaction of the $x^2-y^2$ metal orbital with the hybrid orbital in sulfur. Ab initio calculations have been carried out to explore the ring inversion process for the model $Cl_2TiS_3$ compound. We have optimized $C_s$ and $C_{2v}$ structures of the model compound at the RHF level. The energy barriers for the ring inversion are sensitive to the used basis set. With 4-31$G^*$ for the Cl and S ligands, the barriers are computed to be 8.41 kcal/mol at MP2 and 8.02 kcal/mol at MP4 level.

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References

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