Structures and N¡æSi Bond Characters of 1-Fluorosilatrane and the Silatranyl Cation

Bulletin of the Korean chemical society

Youngkyu Do¹  Yoon Sup Lee¹  Cheolbeom Bae¹  Hyo Sug Lee¹ 

关键词: 1-Fluorosilatrane;    Silatranyl cation;    Transannular bond;    Ab initio;    Density functional method.;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

The structures of 1-fluorosilatrane and the silatranyl cation were calculated by Hartree-Fock (HF), Mフfller-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℃Si bond distance of 1-fluorosilatrane from the hybrid DFT calculations (~2.32�?) using the Perdew-Wang correlation functional agrees with the gas phase experimental value (2.324�?), while other functionals yield larger distances. The MP2 bond distance (2.287�? with 6-311G^*) is shorter, and the HF one (2.544 �? with 6-311G^*) 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℃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 �? 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.

【 授权许可】

Unknown