Effective Coordination Control by Utilizing the Cavity of Calixarenes

利用杯芳烃空腔进行有效的配位控制

基本信息

批准号：
18550061
负责人：
ISHII Youichi
金额：
$ 2.71万
依托单位：
Chuo University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

项目摘要

Calixarenes are known to serve as a versatile ligand not only with two distinct types of coordination sites, phenolic oxygens and arene rings, but also with an inclusion site (cavity). However, coordination chemistry of transition-metal complexes inside the cavity of calixarenes still remains to be explored. In this study we have investigated two series of calix[4]arene complexes in which the metal centers are located inside the cavity of calix[4]arenes.The reaction of calix[4]arene with [CpRu(CH_3CN)_3]PF_6 in the presence of Et_3N has been found to give the ruthenium-arene type complex [CpRu{calix[4]-(0)(OH)_3}] (1)in good yield. An X-ray diffraction study of complex 1 has revealed that the CpRu+ fragment resides in the cavity of the calix[4]arene ligand, and the Cp protons of 1 exhibit characteristic high-field shift in the ^1H NMR. This fact makes a sharp contrast to the complexation of a Cp*Ru+ fragment with calix[4]arene where the metal center is bound at the outside face of a ph … More enolic ring(complex 2), and 1 can be viewed as a "self-inclusion" product. Further introduction of a Cp*Ru+ fragment into complex 1 gives rise to the inside-outside isomer of [(CpRu)(Cp*Ru){calix[4]-(0)(OH)_3}]+ (3), while introduction of a CpRu+ into 2 leads to its outside-outside isomer. These results indicates that the CpRu+ moiety is first coordinates at the outside face of a calixarene molecule, and then the ring inversion of the calixarene skeleton affords the inside coordination product.On the other hand, when [Ph_4P][ReO_2{p-tBu-calix[4]-(0)_4}] (4)is treated with a variety of cationic transition metal complex ML+, the phenoxo-bridged Re-M complexes [ReO_2{p-tBu-calix[4]-(0)_4}ML] (5a, ML = Cu(NCMe); 5b, Ag(Me2C0); 5c, Au(Ppha); 5d, Rh(cod)) can be obtained in good yield. The heterodinuclear core of complex 5a is located inside the cavity and have revealed to show unique spectral and chemical behaviors. For example, complex 5a undergoes selective alkyne incorporation, while complex 5d undergoes solvent-dependent isomerization to π-arene type regioisomers. Less

钙钙棒烯被称为多功能配体，不仅具有两种不同类型的协调位点，酚类氧和芳烃环，而且还具有包含位点（腔）。然而，钙棒烯腔内过渡金属复合物的协调化学仍有待探索。在这项研究中，我们研究了两个系列的钙棒烯[4]芳烃复合物，其中金属中心位于卡利利片中[4]领域内。Calix[4] Arenene与[CPRU（CH_3CN）_3] PF_6的反应在ET_3N的情况下可以使ruthenium-ruthenium型复杂型ruthenium-Arene型复杂。 [Cpru {Calix [4] - （0）（OH）_3}]（1）良好的收率。复合物1的X射线衍射研究表明，CPRU+片段驻留在Calix [4] Arenene配体的腔中，而在 ^1H NMR中的1个暴露特征高场移的CP质子。这一事实与Cp*ru+片段与Calix [4] Arene的络合形成了鲜明的对比，其中金属中心在pH的外部绑定在pH…更多的enolocy环（复杂2），而1则可以看作是“自我灌注”产品。将Cp*ru+片段进一步引入复合物1导致[（CPRU）（CP*RU）的内部异构体{Calix [4] - （0） - （OH）_3}]+（3），而将CPRU+引入2个导致其外部外部异构体。这些结果表明，CPRU+部分首先是在钙候分子的外侧进行配位，然后在[ph_4p] [ph_4p] [reo_2 {ph_4p] [reo_2 {p-tbu-calix [4] - （0） - （0）_（0）_44}（4）时，clixarene骨架的环反转提供了内部配位产品。苯并桥的re-m配合物[ReO_2 {p-tbu-calix [4] - （0）_4} ml]（5a，ml = cu（ncme）; 5b，ag（me2c0）; 5c，au（ppha）; 5d，rh（cod（cod））可以良好地获得。复合物5a的异源性核心位于腔内，并显示出显示独特的光谱和化学行为。例如，复杂的5a经历选择性炔烃公司，而复杂的5D经历了溶剂依赖性异构化与π-芳烃型区域异构体。较少的