Kevin Schwitalla, Zainab Yusufzadeh, Marc Schmidtmann, Rüdiger Beckhaus
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引用次数: 0
Abstract
A new concept for obtaining cationic complexes with triflate counteranions from coordinating triflato ligands was developed. Various routes are leading to titanium(IV) and titanium(III) triflato complexes efficiently. The reactions of pentafulvene titanium complexes with either triflic acid or silver triflate give the corresponding titanium(IV) triflato complexes in excellent yields. Hydrolysis of the titanium(IV) bistriflato complexes leads to cationic aqua complexes via displacement of the triflato ligand, which consequently acts as a noncoordinating anion. A functionalized titanium(IV) monotriflato complex was synthesized by insertion of a nitrile into the Ti-C bond and the triflato ligand was displaced by an NHC. While the titanium(IV) complexes are mostly inert toward substrates, the donor-free titanium(III) triflato complex is a strong Lewis acid and forms various adducts with monodentate Lewis bases. The titanium(III) complex was oxidized by reaction with TEMPO, resulting in a diamagnetic titanium(IV) complex. The reaction with bidentate ligands results in cationic titanium(III) complexes due to displacement of the triflato ligand by the bidentate ligands. Treatment with acetone leads to an aldol reaction of two acetone molecules and the formation of a cationic diacetone alcohol complex.
研究人员提出了一种从配位三氟配体中获得带有三氟反离子的阳离子配合物的新概念。各种方法都能有效地获得三氟化钛(IV)和三氟化钛(III)络合物。五富烯钛络合物与三氟丙烯酸或三氟化银反应,可以得到相应的三氟化钛(IV)络合物,产量极高。双三氟化钛(IV)络合物水解时,三氟化钛配体发生位移,产生阳离子水络合物,从而成为非配位阴离子。通过在钛-碳键中插入一个腈,并用一个 NHC 取代三氟配体,合成了一个功能化的单(IV)三氟钛络合物。钛(IV)络合物对底物大多是惰性的,而不含供体的三氟钛(III)络合物则是一种强路易斯酸,能与单价路易斯碱形成各种加合物。钛(III)络合物通过与 TEMPO 反应被氧化,生成二磁性钛(IV)络合物。与双齿配体反应会产生阳离子钛(III)络合物,原因是双齿配体取代了三氟配体。用丙酮处理会导致两个丙酮分子发生醛醇反应,形成阳离子双丙酮醇复合物。
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.