Fluorenyl Half-Sandwich Bis(tetramethylaluminate) Complexes of the Rare-Earth Metals: Synthesis, Structure, and Isoprene Polymerization
作者:Dominic Diether、Konstantin Tyulyunov、Cäcilia Maichle-Mössmer、Reiner Anwander
DOI:10.1021/acs.organomet.7b00543
日期:2017.12.11
fluorenyl abstraction in lanthanum complexes (Flu)La(AlMe4)2 and (FlutBu)La(AlMe4)2 by trityl borate [Ph3C][B(C6F5)4]. The reaction of half-sandwich complexes (FluR)Ln(AlMe4)2 with equimolar amounts of Me2AlCl did not give access to catalytically active species. Crystallization of binary mixtures (FluSi)Y(AlMe4)2/Me2AlCl in distinct molar ratios of 1:1 and 1:1.7 yielded complexes [(FluSi)Y(AlMe4)(μ-Cl)]2 and
针对(Flu R)Ln(AlMe 4)2型的半三明治复合物,用等摩尔量的R-取代的钾处理均均四甲基铝酸盐Ln(AlMe 4)3(Ln = Y,La,Nd和Lu)芴基。的La(阿尔梅的复分解反应4)3与K(流感)(流感=芴= C 13 H ^ 9)和K(流感吨卜)(流感吨卜=二(叔丁基)芴基)选择性地得到所需的半三明治复合物(Flu R)La(AlMe 4)2。Y(AlMe 4)3与K(Flu)/ K(Flu t Bu)的相应反应和Lu(AlMe 4)3与K(Flu t Bu)的相应反应产生了半三明治和三明治复合物的混合物具有K(Flu)的(AlMe 4)3仅产生三茂金属配合物(Flu)2 Lu(AlMe 4)。立体上要求更高的1-三甲基甲硅烷基芴基(Flu Si)允许在整个Ln(III)尺寸范围(Ln = La,Nd,Y和Lu)中分离半夹心络合物,结晶产率高达94%。用常规使用的硼酸盐或硼烷活化剂活化后[Ph3