Crossing Organolithium Compounds with Organolithium Compounds: Molecular Squares and a Cage-Encapsulating Reaction
作者:Andrew A. Fyfe、Alan R. Kennedy、Jan Klett、Robert E. Mulvey
DOI:10.1002/anie.201103027
日期:2011.8.16
extraordinary crossing reaction involving three popular utility organolithium reagents nBuLi, LiTMP (TMP=2,2,6,6‐tetramethylpiperidide), and LiC5H5 leads to the unexpected deprotonation of C5H5− anions to C5H42− dianions, which was manifested through the trapping of the hexameric nBuLi cage by a [Li(μ‐TMP)Li(μ‐C5H5)}4] molecular square ring (see picture).
Investigations into the reactivity of lithium indenyl with alpha diimines with chlorinated backbones and formation of related functional ligands and metal complexes
作者:Chi-Tien Chen、Mark E. Fischer、Caroline Windsor、Ino C. Vei、David G. Calatayud、Malcolm L.H. Green、Sofia I. Pascu
DOI:10.1016/j.poly.2016.09.021
日期:2016.11
and a chlorine substituted alpha diimine of the form [Cl(NPh)2}C)]2 unexpectedly yielded the corresponding NH rearranged derivative [PhN(H)C(C9H6)]2 (1) rather than the predicted symmetrical α-diimine. This compound 1 was characterised by 1H NMR, 13C1H} NMR and mass spectrometry, and additionally by X-ray diffraction. It was found that 1 was the first indene-substituted and symmetric secondary amine
摘要茚基锂与[Cl(NPh)2} C)] 2形式的氯取代的α二亚胺之间的反应出乎意料地产生了相应的NH重排衍生物[PhN(H)C(C9H6)] 2(1),而不是预测对称的α-二亚胺。该化合物1通过1 H NMR,13 C 1H} NMR和质谱以及另外通过X射线衍射进行表征。发现1是第一个被茚取代的对称仲胺,它在DMSO中也具有很高的荧光性。已经研究了1对基于MX2片段的简单无机和有机金属过渡金属前体的反应性,其中M =第10组金属,X =卤化物或甲基。出奇,与[PtMe2(COD)]的反应导致在C–C配体主链上结合的茚基与新配体(2)之间的偶联反应被发现,试图合成金属连接的二胺。单晶X射线衍射研究证实了该化合物2在固态下具有耦合的茚基残基和离域的C-C键。通过X射线晶体学进行的结构鉴定表明,化合物2是非常稀少的扁平和扩展的芳族有机分子的实例,通过质谱和质谱分析,红外光谱和核磁共振光谱可
The combination of mononuclear metallocene and phenoxyimine complexes to give trinuclear catalysts for the polymerization of ethylene
作者:Christian Görl、Helmut G. Alt
DOI:10.1016/j.jorganchem.2007.10.001
日期:2007.12
Trinuclear complexes were synthesized by combination of metallocene and phenoxyimine zirconium complexes. After activation with methylalumoxane (MAO), these catalysts polymerize ethylene with moderate and good activities. Due to the presence of different catalytic centers, polyethylenes with broad or bimodal molecular weight distributions were obtained.
Fulvene, metallocene catalysts and preparation method thereof, and preparation of polyolefines copolymer using the same
申请人:Park Young-Whan
公开号:US20050004385A1
公开(公告)日:2005-01-06
The present invention relates to a novel fulvene compound and a preparation method thereof, and more particularly to a fulvene compound having substituted groups in the 2- and 5-positions, prepared from an unsaturated ketone having a substituted group in the β-position and a halogen atom in the α-position, and a preparation method thereof. The present invention also relates to a metallocene catalyst having a substituted group in the α-position carbon of the bridge of the cyclopentadienyl group only by reaction of a fulvene compound and an anion group including the cyclopentadienyl group, and a preparation method of a polyolefin copolymer using the same.
Synthesis, Electronic Structure, and Reactivity of Palladium(I) Dimers with Bridging Allyl, Cyclopentadienyl, and Indenyl Ligands
作者:Matthew J. Chalkley、Louise M. Guard、Nilay Hazari、Peter Hofmann、Damian P. Hruszkewycz、Timothy J. Schmeier、Michael K. Takase
DOI:10.1021/om400415c
日期:2013.8.12
identity of the bridging ligand. As a result of different overlap between the metal centers and the π orbitals of the bridging allyl, Cp, or indenylligand, Cp ligands are more likely to result in an anti relationship between the two bridging ligands, while allyl and indenylligands are more likely to give a syn relationship. The solid-state structures indicate that bridging allyl ligands bind the most tightly
合成三个新的Pd(I)二聚体(μ-All)(μ-Cp)Pd(PEt 3)} 2(All = C 3 H 5,Cp = C 5 H 5),(μ-All) (μ-Ind)Pd(PEt 3)} 2(Ind = C 7 H 9)和(μ-Cp)(μ-Ind)Pd(PEt 3)} 2,其中包含桥接的烯丙基,据报道,Cp或茚基配体均由三乙基膦作为辅助配体支撑。这些新化合物的固态几何形状,电子结构和反应性已与二聚体(μ-All)2 Pd(PEt 3)} 2进行了比较。和(μ-Cp)2 Pd(PEt 3)} 2,以前已经报道过。这项工作建立了包含桥接烯丙基,Cp或茚基配体的配合物的固态和电子结构有许多相似之处。例如,在所有情况下,桥联配体通过三个碳原子与两个Pd原子键合,只有桥联基团的中心碳原子与两个金属中心键合。但是,基于桥接配体的身份也存在重要差异。由于金属中心与桥接烯丙基,Cp或茚基配体的π