STRACTURAL INVESTIGATION OF GRIGNARD REAGENTS BY MEANS OF SPRAY IONIZATION MASS SPECTROMETRY AND RAPID X-RAY CRYSTALLOGRAPHY

喷雾电离质谱和快速X射线晶体学对格氏试剂的结构研究

• 批准号: 10671983
• 负责人: YAMAGUCHI Kentaro
• 金额: $ 1.15万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10671983/
• 关键词: Grignard reagent; X-ray crystallography; ESI-MS; equilibrium; CCD回折計; 有機金属試薬

The cold ESI, operating ionization under low temperature was recently developed in our laboratory and proved to be effective to preserve thermally unstable compounds unchanged. Some significant spectra were obtained form MeMgCl, MeMgBr, EtMgCl, EtMgBr, PhMgCl t-BuMgCl, AllyMgCl and i-PrMgCl in tetrahydrofuran (THF) solution using the cold ESI. The characteristic ion peaks consistent with these three spectra of m/z 529, 601 and 673 indicate the ion species of [NMgィイD22ィエD2ClィイD23ィエD2(THF)ィイD2nィエD2]ィイD1+ィエD1 formed based on the atomic nitrogen attached break down products. The [RMgィイD22ィエD2ClィイD23ィエD2(THF)ィイD2nィエD2-H]ィイD1+ィエD1 ion peaks directly related to the corresponding Grignard species are definitely observed in EtMgCl and PhMgCl. The isotopic ion peak patterns as well as MS/MS analysis detecting sequential THF cleavage from the parent ion suggest these ion structures. Following equilibrium is then derived.3RMgX(THF)ィイD2nィエD2【double arrow】RィイD22ィエD2Mg + RMgィイD22ィエD2XィイD23ィエD2(THF)ィイ … More D2nィエD2 (eq.1)On the other hand, X-ray crystallographic analyses were undertaken. We determined the crystal structures of 2[MgィイD22ィエD2ClィイD23ィエD2(THF)ィイD26ィエD2]・[PhィイD24ィエD2MgィイD22ィエD2ClィイD22ィエD2] obtained from PhMgCl, and [MgィイD22ィエD2ClィイD23ィエD2(THF)ィイD26ィエD2]・[t-BuMgClィイD22ィエD2(THF)] from t-BuMgCl. The structure of dimagnesium cationic species included in the both crystals obtained from PhMgCl and t-BuMgCl was solved. This cationic species [MgィイD22ィエD2ClィイD23ィエD2(THF)ィイD26ィエD2]ィイD1+ィエD1 which is detected in the Grignard reagent for the first time has rarely observed. The first crysta lstructure of RMgX without solvent molecule was observed. In case of the crystal obtained from t-BuMgCl, monomeric structure (t-BuMgClィイD22ィエD2THF) was observed together with the cationic species. These constitutions were thought to be included in the Schlenk equilibrium.8PhMgCl(THF)ィイD2nィエD2 【double arrow】2PhィイD22ィエD2Mg + 2[(MgィイD22ィエD2ClィイD23ィエD2)(THF)ィイD26ィエD2]ィイD1+ィエD1 + [PhィイD24ィエD2MgィイD22ィエD2ClィイD22ィエD2]ィイD12-ィエD1 (eq. 2)5t-BuMgCl(THF)ィイD2nィエD2 【double arrow】 2t-BuィイD22ィエD2Mg + [(MgィイD22ィエD2ClィイD23ィエD2)(THF)ィイD26ィエD2]ィイD1+ィエD1 + [t-BuMgClィイD22ィエD2(THF)]ィイD1-ィエD1 (eq. 3)Other crystal structures of Grignard species have also been investigated in the same manner for comparison. In case of MeMgCl, the crystal structure of MeィイD22ィエD2MgィイD24ィエD2ClィイD26ィエD2(THF)ィイD26ィエD2 included in Schlenk equilibrium was found.6MeMgCl(THF)ィイD2nィエD2 【double arrow】 2MeィイD22ィエD2Mg + MeィイD22ィエD2MgィイD24ィエD2ClィイD26ィエD2(THF)ィイD26ィエD2 (eq. 4) Less

冷ESI是本实验室最近发展起来的一种低温电离技术，它能有效地保存热不稳定化合物。在四氢呋喃（THF）溶液中，MeMgCl、MeMgBr、EtMgCl、EtMgBr、PhMgCl、t-BuMgCl、AllyMgCl和i-PrMgCl在冷ESI下得到了一些有意义的光谱。与m/z 529、601和673的这三个光谱一致的特征离子峰表明基于原子氮附着的分解产物形成的[NMg双D22双D2Cl双D23双D2（THF）双D2 n双D2]双D1+双D1的离子种类。在EtMgCl和PhMgCl中明确地观察到与相应的格氏物种直接相关的[RMg] D22 [D2Cl] D23 [D2（THF）] D2 n [D2-H][D1+ D1]离子峰。同位素离子峰型以及MS/MS分析检测到从母离子的连续THF裂解表明这些离子结构。然后推导出以下平衡。3RMgX（THF）δ D2 n δ D2[双箭头]R δ D22 δ D2 Mg + RMg δ D22 δ D2 X δ D23 δ D2（THF）δ ...更多信息 另一方面，进行X射线晶体学分析。我们测定了从PhMgCl得到的2[Mg（OH）2 D22 D2Cl D23 D23 D2（THF）D26 D26 D2]·[Ph（OH）2 D24 D2 Mg（OH）2 D22 D2Cl D22 D22 D2]和从t-BuMgCl得到的2 [Mg（OH）2 D22 D2Cl D23 D24 D2（THF）D26 D2]·[t-BuMgCl D22 D22 D2（THF）]的晶体结构。从PhMgCl和t-BuMgCl得到的两种晶体中包含的二镁阳离子物种的结构得到解决。这种首次在格氏试剂中检测到的阳离子物种[Mg（OH）2 D22 D2Cl D23 D23 D2（THF）D26 D26 D2] D1+ D2 D1很少被观察到。观察到了不含溶剂分子的RMgX的第一晶体结构。在从t-BuMgCl获得的晶体的情况下，观察到单体结构（t-BuMgCl·D22·D2 THF）以及阳离子物质。8PhMgCl（THF）β-D2n β-D2 [双箭头]2Ph β-D22 β-D2Mg + 2[（Mg β-D22 β-D2Cl β-D23 β-D2）（THF）β-D26 β-D2] β-D1+ β-D1 + [Ph β-D24 β-D2Mg β-D22 β-D2Cl β-D22 β-D2] β-D12-β-D1（eq. 2）5 t-BuMgCl（THF）双D2 n双D2 [双箭头] 2 t-BuMgCl双D22双D2 Mg + [（Mg双D22双D2Cl双D23双D2）（THF）双D26双D2]双D1+双D1 + [t-BuMgCl双D22双D2（THF）]双D1-双D1（eq. 3)为了比较，也以相同的方式研究了格利雅物种的其他晶体结构。在MeMgCl的情况下，发现Schlenk平衡中包括的Me 22-D2 Mg 22-D2 Mg 24-D2Cl-D26-D26-D2（THF）-D26-D2的晶体结构。4)少

项目成果

S.-G.Roh,K.-M.Park,G.-J.Park,S.Sakamoto,K.Yamaguchi and K.Kim: "Synthesis of a Five-Membered Molecular Necklace[5]MN : A2+2 approach"Angew. Chem. Int. Ed.. 38. 637-641 (1999)

S.-G.Roh、K.-M.Park、G.-J.Park、S.Sakamoto、K.Yamaguchi 和 K.Kim：“五元分子项链[5]MN 的合成：A2 2 方法

S. Sakamoto, M. Fujita, K. Kim and K. Yamaguchi: "Characterization of Self-assembling Nano-sized Structures by Means of Coldspray Ionization Mass Spectrometry"Tetrahedron. 56. 955-964 (2000)

S. Sakamoto、M. Fujita、K. Kim 和 K. Yamaguchi：“通过冷喷雾电离质谱法表征自组装纳米结构”四面体。

H.Tsuruta,K.Yamaguchi and T.Imamoto: "Evaluation of the Relative Lewis Acidities of Rear Earth (III) Compounds by Tandem Mass Spectrometry"Chem. Commun.. 1999. 1703-1704 (1999)

H.Tsuruta、K.Yamaguchi 和 T.Imamoto：“通过串联质谱法评估稀土 (III) 化合物的相对路易斯酸度”Chem。

H. Kagechika, I. Azumaya, A. Tanatani, K. Yamaguchi and K. Shudo: "A Layered Artificial Dinucleotide Complex."Tetrahedron Lett.. 40. 3423-3426 (1999)

H. Kagechika、I. Azumaya、A. Tanatani、K. Yamaguchi 和 K. Shudo：“层状人工二核苷酸复合物”。Tetrahedron Lett.. 40. 3423-3426 (1999)

K.Yamaguchi,S.Sakamoto,T.Imamoto and S.Ishikawa: "Internal Calibrant for Exact Mass Measurement in Electrospray Inization Mass Spectrometry"Anal. Sci.. 15. 1037-1038 (1999)

K.Yamaguchi、S.Sakamoto、T.Imamoto 和 S.Ishikawa：“电喷雾质谱中精确质量测量的内部校准物”分析。