Molecular Structure of a Monomeric, Base-Free Metal(I) Amide, TlN[Si(CH(3))(3)](2), by Gas Electron Diffraction and by Density Functional Theory and ab Initio MP2 Calculations.
Molecular Structure of a Monomeric, Base-Free Metal(I) Amide, TlN[Si(CH(3))(3)](2), by Gas Electron Diffraction and by Density Functional Theory and ab Initio MP2 Calculations.
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通过气体电子衍射、密度泛函理论和从头算 MP2 计算得出单体无碱金属 (I) 酰胺 TlN[Si(CH(3))(3)](2) 的分子结构。
DOI：
10.1021/ic981217l
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发表时间：
1999
影响因子：
4.6
通讯作者：
K. Klinkhammer
中科院分区：
文献类型：
--
作者：
A. Haaland;Dmitry J. Shorokhov;H. V. Volden;K. Klinkhammer
二（三甲基硅基）氨基铊是气相中的单体。分子对称性为C（2），通过气体电子衍射，T1-N键长为214.8（12）μ m，而结晶二聚体中约为258 μ m（Klinkhammer，K. W的; Henkel，S. J. Organomet. 1994，480，167）。用T1原子上的ECP基组通过DFT或从头算（MP 2）计算的结构优化未能再现实验T1-N键距，除非明确描述金属上的5s、5 p、5d电子并且原子基组包括极化和扩散函数。
Thallium bis(trimethylsilyl)amide is a monomer in the gas phase. The molecular symmetry is C(2), the Tl-N bond length is 214.8(12) pm by gas electron diffraction as compared to about 258 pm in the crystalline dimer (Klinkhammer, K. W.; Henkel, S. J. Organomet. Chem. 1994, 480, 167). Structure optimization by DFT or ab initio (MP2) calculations with the ECP basis set on the Tl atom fails to reproduce the experimental Tl-N bond distance unless the 5s,5p,5d electrons on the metal are described explicitly and the atomic basis set includes both polarization and diffuse functions.