Design for Novel Organo Hypervalent Compounds

新型有机高价化合物的设计

• 批准号: 11304044
• 负责人: TAKAHASHI Masashi
• 金额: $ 23.81万
• 依托单位: TOHO UNIVERSITY (2000)Hiroshima University (1999)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A).
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11304044/
• 关键词: hypervalent; pentacoordinate carbon species; pentacoordinate boron species; phophorane; phosphorus; arsenic; antimony; porphyrin; アンチアピコフィリシティー; 反結合性P-O軌道; メスバウアー分光; ハイパーバレント; S_N2反応

Porphyrin complexes of group 15 : A equilibrium mixture of [(OEP)P(R)(OH)]^4Cl^-(10) and (OEP)PR(=O)(1)was obtained by the reaction of RPCl_2(R=Me, Et, Ph) and (OEP)H_2. Since the acidity of the OH group in 10 is high, 1 and 10 are selectively isolated by controlling pH for the solution of the mixture. The existence of P=O double bond in 1 is confirmed by the X-ray structural dctermination. (OEP) As (R)(=O)(14) is also obtained via [(OEP)As(R)(OH)]^<6+>X^- (13). 13 is the first arsenic porphyrin whose molecular structure is confirmed by X-ray crystallography. The acid-base equibrium between 14 and 13 is also observed. NMR indicates that the acidity of 13 is weaker than that of 10. The heterobimetallic μ-oxo porphyrins [(OEP)Al-O-E(OEP)(R)] (E=P, As) are derived by the reaction of [(OEP)Al(Me)] and the hydroxo porphyrins. The corresponding Al-Sb dinuclear porphyrin is obtained by a photo reaction. The formation of exciplex under the irradiation of light is suggested. ^<121>Sb Mossbauer … More spectra for Sb-TPP complexes indicate that the electronic state of Sb is strongly affected by the axial ligands.Novel hypervalent pentacoordinate carbon and boron compounds : A stable pentacoordinate carbon compound [(MeO)_2C(DMA)]^+ having a 1,8-dimethoxyanthracene ((DMA)H) as a tridentate ligand is firstly isolated. The X-ray analysis definitely indicates the existence of O-C-O hypervalent bond and the density function theory (DFT) calculation also indicates the bonding interaction between C-O bond. The hypervalent pentacoordinate boron compound [(CAT)B(DMA)] (CAT=catecolate anion) is also prepared and fully specificated using an X-ray determination, ^<11>B NMR and a DFT calculation. Employing the van Koten type ligand as a flexible ligand, the second example of hypervalent carbon contpound is obtained and characterized.anti-apicophilic phosphoranes : The anti-apicophilic spirophosphoranes having two Martin ligands (2 : O-cis) are obtained as kinetic products. 2 is highly nucleophilic compared to the apicophilic isomer (O-trans). The acidity of α-proton is high for 2, and by the reaction of its anion and benzaldehyde a hexacoordinate compound, being the intermediate species for Wittig reaction, is derived. No such a product is obtained for apicophilic isomer. Less

第15组的卟啉复合物：[（OEP）P（r）（OH）]^4Cl^ - （10）和（OEP）PR（= O）（1）的等效混合物是通过RPCL_2（R = ME，ET，ET，pH）和（OEP）H_2的反应获得的。由于OH组在10中的酸度很高，因此通过控制混合物溶液来选择性地分离1和10。 X射线结构DC端到确认了1中P = O双键的存在。 （OEP）AS（r）（= o）（14）也通过[（OEP）为（R）（OH）]^<6+> X^ - （13）获得。 13是第一个砷卟啉，其分子结构通过X射线晶体学证实。还观察到14至13之间的酸碱等效物。 NMR表明13的酸度弱于10。异金属金属μ-oxo卟啉[（OEP）al-O-e（OEP）（r）]（e = p，aS）是通过[（OEP）Al（Me）]和羟基卟啉的反应得出的。相应的Al-SB双核卟啉是通过照片反应获得的。建议在光照射下形成弹药。 ^<121>Sb Mossbauer … More spectra for Sb-TPP complexes indicate that the electronic state of Sb is strongly affected by the axial ligands.Novel hypervalent pentacoordinate carbon and boron compounds: A stable pentacoordinate carbon compound [(MeO)_2C(DMA)]^+ having a 1,8-dimethoxyanthracene ((DMA)H) as首先是隔离的三叉戟配体。 X射线分析清楚地表明存在O-C-O高估键，密度函数理论（DFT）计算也表明C-O键之间的键合相互作用。还可以使用X射线测定， ^<11> b NMR和DFT计算，制备了高价值的五级硼化合物[（CAT）B（DMA）]]（CAT = catecaly阴离子）。采用Van Koten型配体作为柔性配体，获得了高价值碳续的第二个例子并进行表征。具有两个Martin配体（2：o-CIS）的抗性磷酸磷酸化是动力学的。与亲粒性异构体（O-Trans）相比，2是高核颗粒志。 α-蛋白的酸度高为2，并且通过其阴离子和苯甲醛A己醛化合物的反应，是Wittig反应的中间物种。没有用于寄生虫异构体的产物。较少的

项目成果

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