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

最近在我们的实验室中开发了低温下的冷ESI，在低温下进行了电离，并被证明可有效保存不变的不稳定化合物。使用冷ESI，在四氢呋喃（THF）溶液中获得了MEMGCL，MEMGBR，ETMGCL，ETMGBR，PHMGCL T-BUMGCL，ALLYMGCL和I-PRMGCL的一些显着光谱。特征离子峰与M/z 529、601和673的这三个光谱一致，表明[NMGCL和PHMGCL的离子物种。同位素离子峰模式以及MS/MS分析检测来自父离子的顺序THF裂解表明这些离子结构。然后得出等效后的后面。3rmgx（THF）II D2NIE D2【双箭头】rii D222nie D2MG + RMGI D22XII D23I D2（THF）II…更多D2Nie D2（EQ.1），另一方面，X-Ray Crellallocraphic Analyake the Outteraken。我们确定了2 [MGCL D22CL D23D2（THF）D26E D2] ・ [PHMGCL D24D2MGCL D22CL D22E D2]的晶体结构，从PHMGCL获得，和[MGCL D22CL D22CL D222（THF）D26E D2 D2] D2-BUMGCL d2 d2 d2 ef tff d22e tff d2 d2 eft tfmgcl。从PHMGCL和T-BUMGCL获得的两种晶体中都包含二肽阳离子物种的结构。这种阳离子物种[MGI D22E D2CLI D23E D2（THF）I D26E D2] I D1+E D1在Grignard试剂中首次检测到的D1+E D1很少观察到。观察到没有解决分子的RMGX的第一个晶体L结构。如果从T-BumgCl获得的晶体，则观察到单体结构（T-Bumgcli D22E D2THF）与阳离子物种一起观察到。这些配置被认为包含在Schlenk等效brium中。8phmgcl（THF）II D2NIE D2 [Double Arrow] 2Phi D22 mg + 2 [（MGCLD22线索D23线索D2） D22] II D12-线索D1（等式2）5T-BUMGCL（THF）II D2NIE D2 [双箭头] 2T-BUMGD22 mg + [（MGCL D22CL D23CL D2）（MGCL D22CL D2CL D2）（THF）D26CL D2 D2] D1 + D1 + D1 + D1 + D1 + D1 + D1 + [T-BUMGCL D22 CLL D2 CLL D1 D1 D1 D1 D1 D1 D1（TH）d1（f）d1（f）还以相同的方式研究了grignard物种以进行比较。如果是MEMGCL，则发现了Schlenk等价brium的MEMGCL D22MGCL D22CL D26D2（THF）D26D2。 D26YD2（等式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)

F.Ibukuro,M.Fujita,K.Yamaguchi and J.-P.Sauvage: "Quantitative and Spontaneous Formation of a Doubly Interlocking [2] Catenane Using Copper(I) and Palladium(II) as Templating and Assembling Centers"J. Am. Chem. Soc.. 121. 11014-11015 (1999)

F.Ibukuro、M.Fujita、K.Yamaguchi 和 J.-P.Sauvage：“使用铜 (I) 和钯 (II) 作为模板和组装中心定量和自发形成双联锁 [2] 链烷”J。