Peresypkina Eugenia, Heindl Claudia, Virovets Alexander, Brake Helena, Mädl Eric, Scheer Manfred
Institut für Anorganische Chemie, Universität Regensburg, 93040, Regensburg, Germany.
Nikolaev Institute of Inorganic Chemistry, Siberian Division of RAS, Acad. Lavrentyev Straße 3, 630090, Novosibirsk, Russia.
Chemistry. 2018 Feb 16;24(10):2503-2508. doi: 10.1002/chem.201705883. Epub 2018 Jan 25.
Pentaphosphaferrocene [Cp*Fe(η -P )] (1 a) represents an excellent building block for the template-directed synthesis of spherical supramolecules. Here, the self-assembly of 1 a with Cu and Cu halides in the presence of the template complexes [FeCp ][PF ], [CoCp ][PF ] and [CoCp ] is reported, testifying to the redox behavior of the formed supramolecules. The oxidation or reduction capacity of these reactive complexes does not inhibit their template impact and, for the first time, the cationic metallocene [CoCp ] is enclosed in unprecedented anionic organometallic hosts. Furthermore, the large variety of structural motifs, as icosahedral, trigonal antiprismatic, cuboidal and tetragonal antiprismatic arrangements of 1 a units are realized in the supramolecules [FeCp ]@[{1 a} (CuBr) ] (3), [CoCp ] {[CoCp ] @[{1 a} Cu Br (CH CN) ] } (4), {[Cp Co] @[{1 a} (CuI) (CH CN) ]}{[Cp Co] @[{1 a)} Cu I (CH CN) ] } (5), and [{1 a} {(1 a) NH} Cu I (CH CN) ] (6), respectively.
五磷代二茂铁[Cp*Fe(η -P )] (1 a)是用于模板导向合成球形超分子的优良构建单元。本文报道了1 a在模板配合物[FeCp ][PF ]、[CoCp ][PF ]和[CoCp ]存在下与铜及卤化铜的自组装，证明了所形成超分子的氧化还原行为。这些活性配合物的氧化或还原能力并不影响它们的模板作用，并且首次将阳离子金属茂[CoCp ]封装在前所未有的阴离子有机金属主体中。此外，超分子[FeCp ]@[{1 a} (CuBr) ] (3)、[CoCp ] {[CoCp ] @[{1 a} Cu Br (CH CN) ] } (4)、{[Cp Co] @[{1 a} (CuI) (CH CN) ]}{[Cp Co] @[{1 a)} Cu I (CH CN) ] } (5)和[{1 a} {(1 a) NH} Cu I (CH CN) ] (6)中分别实现了多种结构 motif，如1 a单元的二十面体、三角反棱柱体、立方和四方反棱柱体排列。
