Time and Sfcace Control of Reactive Complexes of Carbon and Heavy-Elements

碳与重元素反应配合物的时间和空间控制

• 批准号: 14078220
• 负责人: YAMAMOTO Yohsuke
• 金额: $ 15.36万
• 依托单位: Hiroshima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14078220/
• 关键词: hypervalent; carbon; boron; 高配位; 硫黄配位子; X線解析; 超原子価化合物; 6配位炭素; チオキサントン; アレン; ビニル位S_N2反応; 合成; 3座配位子; エックス線解析

Recently, we reported synthesis and isolation of hypervalent pentacoordinate carbon compounds and hypervalent pentacoordinate boron compounds bearing a rigid anthracene skeleton and a relatively flexible van Koten skeleton. Although the X-ray analysis and density functional calculation of these compounds clearly showed the attractive interaction between the central carbon (boron) and the two coordinating oxygen atoms, these interactions are weak based on the distance and the values from AIM analysis. Thus, we designed a novel tridentate ligand bearing a benzene ring condensed with two seven membered rings in the hope of stronger interaction between the central atom and the coordinating sulfur atoms. We could obtain pentacoordinate carbon compound, but tetracoordinate compounds, where only one of the sulfur atom was coordinating toward the central carbon, were also obtained by changing the substituents on the central carbon atom.

近年来，我们合成并分离了具有刚性蒽骨架和相对柔性van Koten骨架的高价五配位碳化合物和高价五配位硼化合物。虽然这些化合物的x射线分析和密度泛函计算清楚地显示了中心碳（硼）和两个配位氧原子之间的吸引相互作用，但从距离和AIM分析的值来看，这些相互作用是弱的。因此，我们设计了一种新型的三叉齿配体，该配体带有一个苯环，由两个七元环缩合而成，希望中心原子与配位硫原子之间的相互作用更强。我们可以得到五配位碳化合物，但是通过改变中心碳原子上的取代基，也可以得到只有一个硫原子与中心碳配位的四配位碳化合物。

项目成果

山本陽介: "超原子価5配位炭素およびホウ素の合成"化学と工業. 56. 971-972 (2003)

Yosuke Yamamoto：“超价五配位碳和硼的合成”化学与工业 56. 971-972 (2003)。

Syntheses and Structures of Hypervalent Pentacoordinate Carbon and Boron Compounds Bearing an Anthracene Skeleton-Elucidation of Hyperavalent Interaction Based on X-ray Analysis and DFT Calculation

具有蒽骨架的高价五配位碳硼化合物的合成和结构——基于X射线分析和DFT计算的超价相互作用的阐明

• 发表时间: 2005
• 期刊: Journal of the American Chemical Society 127
• 作者: Yamashita;M.; Yamamoto;Y.; Akiba;K.-y.; Hashizume;D.; Iwasaki;F.; Takagi;N.; Nagase;S.
• 通讯作者: S.

Synthesis and characterization of stable hypervalent carbon compounds (10-C-5) bearing a 2,6-bis(p-substituted phenyloxymethyl)benzene ligand

• DOI: 10.1021/ja043802t
• 发表时间: 2005-04-27
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Akiba, KY;Moriyama, Y;Nagase, S
• 通讯作者: Nagase, S

Synthesis and Structure of 16 π Octaalkyltetraphenylporphyrins

• DOI: 10.1021/ja052842
• 发表时间: 2005-09
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Yohsuke Yamamoto;A. Yamamoto;S. Furuta;M. Horie;M. Kodama;Wataru Sato;K. Akiba;S. Tsuzuki;T. Uchimaru;D. Hashizume;F. Iwasaki

S.Matsukawa, K.Kajiyama, S.Kojima, S.-y.Furuta, Y.Yamamoto, K.-y.Akiba: "A New Method for Determining the Difference in Relative Apicophilicity of Carbon Substituents of 10-P-5 Phosphoranes : Disclosure of Solvent Effect on Apicophilicity and Novel Co-cry

S.Matsukawa、K.Kajiyama、S.Kojima、S.-y.Furuta、Y.Yamamoto、K.-y.Akiba：“一种测定 10-P-5 碳取代基相对亲顶端性差异的新方法