Evaluation of Enthalpy Change and Activation Enthalpy of the Reaction of Metal Complexes in Solution

溶液中金属配合物反应的焓变和活化焓的评价

• 批准号: 09640662
• 负责人: AIZAWA Sen-ichi
• 金额: $ 1.79万
• 依托单位: Shizuoka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640662/
• 关键词: Alkylamine; Octahedral-tetrahedral equilibrium; Ligand field stabilization energy; Energy level in spherically symmetric field; Electronic repulsion; Solvent exchange reaction; Activation Enthalpy; 溶媒交換反応速度

The enthalpy differences (DELTAH^0) of the unique equilibrium between octahedral and tetrahedral cobalt(II) ion have been obtained in some primary alkylamine such as n-propylamine (pa, 36.1*2.3 kJ mol^<-1>), n-hexylamine (34.9*1.0 kJ mol^<-1>), 2-methoxyethylamine (meea, 44.8*3.1 kJ mol^<-1>), and benzylamine (50.1*3.6 kJ mol^<-1>). The differences between energy levels of the six- and four-coordinate Co(II) complexes in the spherically symmetric field (DELTAE_<spher>) in the primary alkylamine solvents have been estimated from the values of deltaH^0 by offsetting the ligand field stabilization energies for the octahedral and tetrahedral geometries obtained from the absorption spectral data. It has been confirmed that the values of DELTAE_<spher> is the decisive factor to determine the value of DELTAH^0 and is largely dependent on the electronic repulsion. This concept has been applied to the discussion about difference in energy levels between ground state and dissociative transition state of the solvent exchange reaction. The comparison between activation enthalpy (DELTAH^*) of the solvent exchange reaction of cobalt(II) ion in pa and meea has experimentally revealed that unexpectedly large rate constants of cobalt(II) ion in pa is attributed to small. DELTAH^* value which results from the strong electronic repulsion in the ground state.

八面体和四面体钴（II）离子之间独特平衡的焓差（Δ H^0）已经在一些伯烷基胺中得到，如正丙胺（pa，36.1*2.3 kJ mol^<-1>）、正己胺（34.9*1.0 kJ mol^<-1>）、2-甲氧基乙胺（meea，44.8*3.1 kJ mol^<-1>）和苄胺（50.1*3.6 kJ mol^<-1>）。六配位和四配位Co（II）配合物在伯烷基胺溶剂中球对称场的能级差（Δ E_0<spher>）是通过抵消从吸收光谱数据中获得的八面体和四面体几何构型的配位场稳定化能而从Δ H^0值估算出来的。已经证实，Δ E_的值<spher>是决定Δ H ^0值的决定性因素，并且在很大程度上取决于电子排斥。并将这一概念应用于溶剂交换反应的基态与离解过渡态能级差的讨论。通过对钴（II）离子在pa和meea中溶剂交换反应的活化焓（Δ H ^*）的比较，实验表明，pa中钴（II）离子的速率常数出乎意料地大，这是由于反应速率常数小。Δ H ^* 值，其由基态中的强电子排斥引起。

项目成果

Takeyoshi Yagyu: "Mechanistic Studies on Cyclopalladation of the Solvated Palladium(II)Complexes with N-Benzyl Triamine Ligands." Bulletin of the Chemical society of Japan. (in press).

Takeyoshi Yagyu：“溶剂化钯 (II) 配合物与 N-苄基三胺配体环钯化的机理研究。”

T.Yagyu: "Electronic Effect of Substituents on Cyclopalladation of the Solvated Palladium (II) Complexes with N-Benzyl Triamine[Pd (Sol) { (4-X-C_6H_4CH_<>) NH (CH_<>) _3NR (CH_2)) _3 NH_2}]^<2+> (Sol=Solvent ; R=Ph, H,Me ; X=H,Et, Me, MeO,Cl, and NO_2)"

T.Yagyu：“取代基对溶剂化钯 (II) 配合物与 N-苄基三胺[Pd (Sol) { (4-X-C_6H_4CH_<>) NH (CH_<>) _3NR (CH_2)) 环钯化的电子效应

Sen-ichi Aizawa: "Variable-Temperature and-Pressure Nitrogen-14 Magnetic Resonance Studies on Solvent Exchange of Nickel (II),Iron (II),and Manganese (II) Ions in Neat 1,3-Propanediamine and n-Propylamine" Bulletin of Chemical society of Japan. 70・7. 1593

Sen-ichi Aizawa：“纯 1,3-丙二胺和正丙胺中镍 (II)、铁 (II) 和锰 (II) 离子溶剂交换的变温压氮 14 磁共振研究”日本化学会公报 70・7。

Sen-ichi Aizawa: "Circular Dichroism Spectrophotometric Determination of Metal Ions by Using Optically Resolved Sparingly Soluble fac(S)-〔Rh(aet)_3〕 (aet=2-Aminoethanethiolate)" Chemistry Letters. 775-776 (1998)

Sen-ichi Aizawa：“使用光学分辨微溶fac(S)-〔Rh(aet)_3〕（aet=2-氨基乙硫醇）测定金属离子”化学快报775-776（1998）。

S.Aizawa: "Variable-Temperature and-Pressure Nitrogen-14 Magnetic Resonance Studies on Solvent Exchange of Nickel (II), Iron (II), and Manganese (II) Ions in Neat 1,3-Propanediamine and n-Propylamine" Bull.Chem.Soc.Jpn.70(7). 1593-1597 (1997)

S.Aizawa：“纯 1,3-丙二胺和正丙胺中镍 (II)、铁 (II) 和锰 (II) 离子溶剂交换的变温压氮 14 磁共振研究”公报