描述了新型的锆和ha的ansa双(茚基)配合物的合成和表征。两个茚基部分通过1,2-双(二甲基甲硅烷基)苯单元在1-,1'-位连接。配体前体是通过三个反应步骤制备的,这些步骤包括氯二甲基硅烷和1,2-二溴苯的格氏偶联,PdCl 2催化的氯化和与茚基锂的反应。通过用n-BuLi对相应的双-(茚基)化合物进行质子化,然后进行MCl 4的金属化反应,可得到锆和ha的配合物。(M = Zr,Hf)在四氢呋喃中。通过单晶X射线衍射分析建立了两种配合物的固态分子结构。在乙烯聚合反应中,两种配合物均表现出高活性。与ha催化剂5(3590kg PE / mol cat.h )相比,锆茂催化剂4显示出更高的活性(7610 kg PE / mol cat.h)。
silyl azides resulted in the formation of triplet states even for those having two or three Si–N3 groups in a molecule. ESR spectra of the silylnitrenes exhibited a part of the fine structure at around 820 mT. All the silyl azides studied gave nearly identical D-values (ca. ) and much larger than those in phenylnitrenes. The results suggested that electron spins are localized in the nitrogen p-orbitals
Phenylenbis(silandiyl-triflate) als neuartige Synthesebausteine für vielfältig strukturierte Organosilizium-Polymere
作者:Wolfram Uhlig
DOI:10.1002/hlca.19940770409
日期:1994.6.29
Phenylenebis(silandiyl triflates) – New Synthetic Building Blocks for Variously Structured Organosilicon Polymers
苯二双(硅烷基三氟甲磺酸酯)–各种结构的有机硅聚合物的新型合成构件
An ESR Study of a Tetrasilaspirobiindane Anion Radical. Stereoelectronic Electron-Accepting Effects of Trialkylsilyl Groups
作者:Wataru Setaka、Chizuko Kabuto、Mitsuo Kira
DOI:10.1246/cl.1999.317
日期:1999.4
ESR spectra of a tetrasilaspirobiindane anionradical (1−) showed a doublet of doublet hfs pattern at low temperatures and significant line-width alternation, indicating that there is remarkable difference in the electron-accepting effects between two silyl substituents at the benzene ring with the unpaired electron due to the ring conformation.
An Efficient Method for the Protection of Aromatic Amines with Benzostabase and Its Utility in Anionic Aromatic Transformations
作者:Donald Weaver、Mark Reed、Erhu Lu、Arun Yadav
DOI:10.1055/s-0033-1339794
日期:——
Herein we describe an efficient and generally applicable method of protecting a diverse series of aromatic amines with the benzostabase' group. We also demonstrate its efficient use in aromatic anionic chemistry including its utility in the anionic ortho Snieckus-Fries rearrangement.
The first successful ring opening polymerization at the SiSi bond: a novel o-(disilanylene)phenylene polymer