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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.

合成了A_2MCl_6（A=C_4H_8NH_2，<10>C_5H_NH_2，C_6H_NH_2<12>; M=Sn，Te，Pt）配合物，用X射线单晶衍射法测定了它们的室温晶体结构。对（C_4H_8NH_2）_2MCl_6进行了~ 1HNMR、~ <35>1Cl NQR和差热分析（DTA和DSC）。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-固相变的机制。通过热分析发现了（<10>C_5H_NH_2）_2MCl_6和（C_6H_NH_2<12>）_2MCl_6的固-固相变，计算了它们的相变温度和相变焓，并对C_4H_8NH_2^+、C_5H_NH_2 ^+和C_6H_NH_2 ^+离子进行了从头算和DFT HF方法的分子轨道计算<10><12>。确定了阳离子的稳定态和过渡态构象及其电能。合成了（C_5H_8NH_2<10>）PF_6、（C_4H_8NH_2）PF_6和（C_4H_8NH_2）ClO_4，并进行了^1H、^2H、^<19>F、^<31>P和^<35>Cl NMR、X射线粉末衍射和热分析（DTA和DSC）。发现了固-固转变，并对其温度和焓变进行了评价。测定<10>了固相中C_5H_NH_2 ^+和C_4H_8NH_2^+离子的运动状态。合成了（C_4H_8NH_2O）（C_6HCl_2O_4），用X射线单晶衍射法测定了其晶体结构。C_4H_8NH_2O^+离子的构象和涉及N-H键的氢键图式。O和O-H...确定了晶体中的O型氢键。