Reseach on Preparation and Properties of the dpcb Ligand and Their Metal Complexes Containing Various Functional Groups

含多种官能团的dpcb配体及其金属配合物的制备及性能研究

基本信息

批准号：
17550027
负责人：
TOYOTA Kozo
金额：
$ 1.73万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2006
项目状态：
已结题

项目摘要

Sterically protected 3,4-diphosphinidenecyclobutenes (hereafter abbreviated to DPCB), bearing an extremely bulky 2,4,6-tri-t-butylphenyl group (abbreviated to the Mes^* group), are unique bidentate ligands of interest, because of their relatively rigid framework containing the phosphorus-carbon π-bond. We have prepared various transition metal complexes of DPCB and some of them were used as homogeneous catalysts. We recently prepared 1,2-di(2-thienyl)-3,4-diphosphinidenecyclobutene (DPCB-T) and 1,2-di(3-thienyI)- congener (DPCB-T'), as well as some polymers bearing repeating unit containing the DPCB-T moiety. Both DPCB-T and DPCB-T are promising building blocks for construction of more elaborate DPCB derivatives, because introduction of functional group (at the position a to the sulfur atom) is expected to be easily performed under mild conditions. In fact, various DPCB-T derivatives were prepared by lithiation with butyllithium followed by reaction with electrophiles. Furthermore, mon … More o-and diiodo-DPCB-T derivatives were obtained by successive reactions of DPCB-T with butyllithium and iodoacetonitrile. Further conversions of the iodo-DPCB-T derivatives were then carried out : Various alkynyl groups, such as trimethylsilylethynyl, pyridylethynyl, or azulenylethynyl, were introduced to give new DPCB ligands. Some novel 3,4-diphosphinidenecyclobutenes, bearing thienyl or azulenyl group at the 1,2-positions, were also prepared. In addition, novel spacer was developed as follows. In the course of our continuing researches on developing novel organophosphorus ligands as mentioned above, we interested in the ligand system containing the 2,3-thienylene spacer. The 2,3-thienylene spacer has an advantage : introduction of substituents or functional groups into the 5-position of the thiophene ring is easy. This advantage will help, for example, researches on sophisticated ligands. We then investigated preparations of 1,4-bis(2-ethynyl-3-thienyl)benzene and its application to pyridine ligands, in which the bis(ethynylthienyl)benezene moiety is incorporated as a spacer. Less

立体保护的3,4-二磷酸烯丙基酮（以下简称为DPCB），具有极大的2,4,6- tri-t-T-T-丁基苯基基团（对MES^*组的缩写），因为它是独特的鸟类配体，因为它们的相对刚好是相对刚好的磷酸化的独特的鸟类配体。我们已经准备了DPCB的各种过渡金属复合物，其中一些被用作均匀的催化剂。我们最近制备了1,2-di（2-硫烯基）-3,4-二磷酸烯环丁烯（DPCB-T）和1,2-di（3-噻纪） - 同型（DPCB-T'），以及一些带有含DPCB-T Moireiety的重复单元的聚合物。 DPCB-T和DPCB-T均被承诺构建更精细的DPCB衍生物的构建块，因为预计在轻度条件下的功能组（位于A到硫原子的位置A位置）很容易执行。实际上，通过用丁乙基丁胺的岩性，然后与电力物反应制备各种DPCB-T衍生物。此外，Mon…通过DPCB-T与丁乙烯岩和碘乙腈的成功反应获得了更多的O-and Diiodo-DPCB-T衍生物。然后进行了iodo-dpcb-t衍生物的进一步转化：引入了各种烷基尼尔基团，例如三甲基甲基甲硅烷基，吡啶基硫基尼尔或硫苯基硫尼尼尔，以提供新的dpcb配体。还制备了一些新型的3,4-二磷酸烯烃，在1,2位置上含有硫烯基或副苯基。此外，新颖的间隔者的开发如下。如上所述，在继续开发新型有机磷配体的研究过程中，我们对含有2,3-甲基乙烯垫片的配体系统感兴趣。有一个优势：将亚电位或官能团引入噻吩环的5位很容易。例如，这种优势将有助于研究复杂的配体。然后，我们研究了1,4-双（2-乙基-3-硫烯基）苯的制剂及其在吡啶配体中的应用，其中将双二烯基（乙基烯基）硅化二苯二苯二聚体部分纳入了间隔剂。较少的

项目成果

期刊论文数量（35）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Preparation and Properties of 1,2-Diferrocenyl Substituted 3,4-Diphosphinidenecyclobutenes and Their Complexes

1,2-二茂铁基取代的3,4-二膦亚膦环丁烯及其配合物的制备及性能

DOI：
发表时间：
2005
期刊：
Organometallics 24・12
影响因子：
0
作者：
H.Tsukamoto;M.Sato;Y.Kondo;Akitake Nakamura;Anil S.Gajare;Subaru Kawasaki;Subaru Kawasaki;Akitake Nakamura;Subaru Kawasaki
通讯作者：
Subaru Kawasaki

Simple and Efficient Preparation of Sterically Protected 1,4-Diphosphafulvenes

空间保护的 1,4-二磷富烯的简单高效制备

DOI：
发表时间：
2005
期刊：
Tetrahedron 61・22
影响因子：
0
作者：
H.Tsukamoto;M.Sato;Y.Kondo;Akitake Nakamura;Anil S.Gajare;Subaru Kawasaki;Subaru Kawasaki;Akitake Nakamura
通讯作者：
Akitake Nakamura

Reaction of 2H- Cyclohepta[b]furan-2-ones with Pyridinium Salts of Trifluoromethanesulfonic Anhydride.

2H-环庚[b]呋喃-2-酮与三氟甲磺酸酐吡啶鎓盐的反应。