Conformations of Cycloalkylammonoium Ions in Crystal

晶体中环烷基铵离子的构象

基本信息

批准号：
10440208
负责人：
ISHIDA Hiroyuki
金额：
$ 0.96万
依托单位：
Okayama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10440208/
关键词：
Nuclear Magnetic Resonance Nuclear Quadrupole Resonance Single Crystal X-ray Diffraction Thermal Analysis Molecular Orbital Calculation Phase Transition Molecular Motion X線回折

项目摘要

A_2MCl_6 complexes (A=C_4H_8NH_2, C_5H_<10>NH_2, C_6H_<12>NH_2 ; M=Sn, Te, Pt) were prepared and their crystal structures at room temperature were determined by single crystal X-ray diffraction. Measurements of ^1H NMR, ^<35>Cl NQR and thermal analysis (DTA and DSC) were made for (C_4H_8NH_2)_2MCl_6. The conformation of C_4H_8NH_2^+ ion, the motions of the cation and the anion, and the mechanism of the solid-solid phase transition were investigated. Solid-solid transitions were found in (C_5H_<10>NH_2)_2MCl_6 and (C_6H_<12>NH_2)_2MCl_6 from thermal analysis and their temperatures and enthalpy changes were evaluated.Molecular orbital calculations (ab initio and DFT-HF methods) were carried out for isolated C_4H_8NH_2^+, C_5H_<10>NH_2^+, and C_6H_<12>NH_2^+ ions. Conformations in stable and transition state and their electric energies were determined for the cations.(C_5H_<10>NH_2) PF_6, (C_4H_8NH_2) PF_6, and (C_4H_8NH_2) ClO_4 were prepared and measurements of ^1H, ^2H, ^<19>F, ^<31>P, and ^<35>Cl NMR, X-ray powder diffraction, and thermal analysis (DTA and DSC) were carried out. Solid-solid transitions were found and their temperatures and enthalpy changes were evaluated. Motional states of C_5H_<10>NH_2^+ and C_4H_8NH_2^+ ions in the solid phases were determined.(C_4H_8NH_2O)(C_6HCl_2O_4) was prepared and the crystal structure was determined at room temperature by single crystal X-ray diffraction. The conformation of C_4H_8NH_2O^+ ion and the hydrogen-bond scheme involving N-H...O and O-H...O type hydrogen bonds in the crystal were determined.

制备了A_2MCl_6配合物(A=C_4H_8NH_2、C_5H_10NH_2、C_6H_12NH_2；M=Sn、Te、Pt)，并通过单晶X射线衍射测定了它们的室温晶体结构。对(C_4H_8NH_2)_2MCl_6进行 1 H NMR、 35 Cl NQR和热分析(DTA和DSC)的测量。研究了C_4H_8NH_2^+离子的构象、阳离子和阴离子的运动以及固-固相变机理。热分析发现(C_5H_<10>NH_2)_2MCl_6和(C_6H_12>NH_2)_2MCl_6存在固-固转变，并评估了它们的温度和焓变。进行了分子轨道计算(从头计算和DFT-HF方法)出孤立的 C_4H_8NH_2^+、C_5H_<10>NH_2^+ 和C_6H_<12>NH_2^+离子。测定了阳离子的稳定态和过渡态构象及其电能。制备了(C_5H_<10>NH_2) PF_6、(C_4H_8NH_2) PF_6和(C_4H_8NH_2) ClO_4并测量了^1H、^2H、^<19> F、 31 P和 35 Cl NMR，进行X射线粉末衍射和热分析（DTA和DSC）。发现了固-固转变并评估了它们的温度和焓变化。测定了固相中C_5H_10>NH_2^+和C_4H_8NH_2^+离子的运动态。制备了(C_4H_8NH_2O)(C_6HCl_2O_4)并在室温下通过单晶X射线衍射确定了晶体结构。确定了C_4H_8NH_2O^+离子的构象以及晶体中N-H...O和O-H...O型氢键的氢键结构。