Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Structures and N→Si Bond Characters of 1-Fluorosilatrane and the Silatranyl Cation

  • Lee, Hyo-Sug (Samsung Advanced Institute of Technology) ;
  • Bae, Cheol-Beom (Department of Chemistry and School of Molecular Science (BK21), Korea Advanced Institute of Science and Technology) ;
  • Do, Young-Kyu (Department of Chemistry and School of Molecular Science (BK21), Korea Advanced Institute of Science and Technology) ;
  • Lee, Yoon-Sup (Department of Chemistry and School of Molecular Science (BK21), Korea Advanced Institute of Science and Technology)
  • Published : 2002.02.20
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Abstract

The structures of 1-fluorosilatrane and the silatranyl cation were calculated by Hartree-Fock (HF), Mofller-Plesset second order (MP2), and various density functional theory (DFT) methods using many different basis sets, demonstrating that the Si-N bonds in two species are quite different. The N${\rightarrow}$Si bond distance of 1-fluorosilatrane from the hybrid DFT calculations $({\sim}2.32{\AA})$ using the Perdew-Wang correlation functional agrees with the gas phase experimental value $(2.324{\AA})$, while other functionals yield larger distances. The MP2 bond distance (2.287${\AA}$ with 6-311$G^{\ast}$) is shorter, and the HF one (2.544 ${\AA}$ with 6-311$G^{\ast}$) larger than those of DFT calculations. The MP2 bond distance is in good agreement with experiment indicating that the electron correlations are crucial for the correct description of the N${\rightarrow}$Si interaction. The silatranyl cation is a stable local minimum on the potential energy surface in all methods employed suggesting that the cation could be a reaction intermediate. The Si-N bond length for the cation is about 1.87 ${\AA}$ for all calculations tested implying that the Si-N bond is mainly conventional. Bonding characteristics of the Si-N bond in two species derived from the natural bond orbital analysis support the above argument based on calculated bond lengths.

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References

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