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Construction of functional supramolecules based on the electronic properties of heteroatoms and nonalternant conjugation

基于杂原子电子性质和非交替共轭的功能超分子的构建

基本信息

批准号：
16550040
负责人：
MURAFUJI Toshihiro
金额：
$ 2.11万
依托单位：
Yamaguchi University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2006
项目状态：
已结题

项目摘要

A nonaltemant organyl ligand derived from azulene, a 1,3-dichloro-2-azulenyl group, is introduced for the first time into the bismuth and antimony center. Conversion of the azulenylbismuthanes into the pentacoordinated difluorides by xenon difluoride promotes the π-polarization of the azulene nucleus, which is detected as a color change in solution as well as changes in the chemical shifts of the ^<13>C NMR spectra. Similar tendency is observed in the antimony congeners. The X-ray crystallographic study of (1,3-dichloro-2-azulenyl)diphenylbismuth difluoride reveals that the intermolecular π-π stacking takes place between the azulenyl groups through the interaction of the five-membered ring with the seven-membered ring. This may reflect the more polarized azulenyl group of the difluorides, which strengthens the stacking interaction.(1,3-Dihalo-2-azulenyl)diphenylphosphines [halogen=Cl,Br] have been synthesized, and the effect of the nonaltemant azulenyl group on the reactivity and properties of these phosphines has been studied in comparison with that of the group 15 congeners. The electronic structure of the nonalternant conjugation is dramatically affected by the change in the valency at the phosphorus. Thus, oxidation of the azulenyldiphenylphosphines with hydrogen peroxide proceeded with a dramatic color change from green to blue, giving the corresponding phosphine oxides. The ^<13>C NMR study shows the enhanced π-polarization in the azulenyl group of the phosphine oxides compared to that of the parent phosphines, but the degree is not as marked as that observed in the bismuth and antimony systems. Azulenylphosphine oxide has head-to-tail π-π stacking in crystals, reflecting the enhanced π-polarization in the high oxidation state of the phosphorus center.

首次在铋和锑中心引入了一个由1，3-二氯-2-甘菊环衍生的有机配体。通过二氟化氙将甘菊环基铋烷转化为五配位二氟化物促进了甘菊环核的π-极化，这被检测为溶液中的颜色变化以及13 C NMR光谱的化学位移的变化<13>。在锑同系物中也观察到类似的趋势。X-射线晶体学研究表明，（1，3-二氯-2-甘菊环基）二苯基二氟化铋的分子间π-π堆积是通过五元环与七元环的相互作用进行的。这可能反映了二氟化物的更极化的奥基，其加强了堆叠相互作用。合成了1，3-二卤-2-奥基）二苯基膦[卤素=Cl，Br]，并与15族同类物进行了比较，研究了奥基对这些膦的反应活性和性能的影响。非交替共轭的电子结构受到磷原子价态变化的显著影响。因此，用过氧化氢氧化甘菊环基二苯基膦，颜色从绿色急剧变化为蓝色，得到相应的氧化膦。13 <13>C NMR研究表明，与母体膦相比，氧化膦的奥基中的π-极化增强，但程度不如铋和锑体系中观察到的那样显著。奥基氧化膦在晶体中具有头-尾π-π堆积，反映了磷中心在高氧化态下增强的π-极化。

项目成果

期刊论文数量（30）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

First introduction of an azulenyl group into the bismuth and antimony center. Synthesis and structure of azulenylbismuthanes and their difluorides.

首先将甘菊环基团引入铋和锑中心。

DOI：
发表时间：
2004
期刊：
Organometallics Vol 23
影响因子：
0
作者：
A.F.M.Mustafizur Rahman;T.Murafuji;K.Kurotobi;Y.Sugihara;N.Azuma
通讯作者：
N.Azuma

Chlorination of p-substituted triarylpnictogens by sulfuryl chloride : Difference in the reactivity and spectroscopic characteristics between bismuth and antimony

磺酰氯氯化对位取代的三芳基硝基化合物：铋和锑之间的反应性和光谱特征的差异

DOI：
发表时间：
2005
期刊：
Journal of Organometallic Chemistry 690
影响因子：
0
作者：
T.Murafuji;T.Azuma;Y.Miyoshi;M.Ishibashi;A.F.M.Mustafizur Rahman;K.Migita;Y.Sugihara;Y.Mikata;T.Murafuji 他;A.F.M.Mustafizur Rahman et al.
通讯作者：
A.F.M.Mustafizur Rahman et al.

Chlorination of p-substituted triarylpnictogens by sulfuryl chloride. Difference in the reactivity and spectroscopic characteristics.

通过磺酰氯对对位取代的三芳基磷进行氯化。

DOI：
发表时间：
2005
期刊：
J.Organomet.Chem. Vol 690
影响因子：
0
作者：
A.F.M.Mustafizur Rahman;T.Murafuji;M.Ishibashi;Y.Miyoshi;Y.Sugihara
通讯作者：
Y.Sugihara

Effect of π-accepting substituent on the reactivity and spectroscopic characteristics of triarylbismuthanes and triarylbismuth dihalides

DOI：
10.1016/j.jorganchem.2004.07.055
发表时间：
2004-10
期刊：
Journal of Organometallic Chemistry
影响因子：
2.3
作者：
A. Rahman;T. Murafuji;M. Ishibashi;Y. Miyoshi;Y. Sugihara
通讯作者：
A. Rahman;T. Murafuji;M. Ishibashi;Y. Miyoshi;Y. Sugihara

Inhibition of Jack bean urease by organobismuth compounds

有机铋化合物对刀豆脲酶的抑制作用

DOI：
发表时间：
2006
期刊：
Bioorganic ＆ Medicinal Chemistry Letters 16
影响因子：
0
作者：
A.F.M.Mustafizur Rahman;T.Murafuji;T.Shibasaki;K.Suetake;K.Kurotobi Y.Sugihara;A.F.M.Mustafuzur Rahman et al.;T.Murafuji et al.
通讯作者：
T.Murafuji et al.