Mietke Thomas, Cruchter Thomas, Winterling Erik, Tripp Matthias, Harms Klaus, Meggers Eric
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany.
Chemistry. 2017 Sep 7;23(50):12363-12371. doi: 10.1002/chem.201701758. Epub 2017 Jul 18.
A straightforward method for post-complexation derivatizations of diastereo- and enantiomerically pure bis-cyclometalated benzoxazole and benzothiazole iridium(III) complexes is reported. Triflate- and bromine-functionalized iridium(III) complex dimers, represented as [Ir(μ-Cl)(C^N) ] , were converted to the corresponding diastereomeric complexes, represented as Ir(C^N) (N^O), using readily available chiral salicyloxazolines and salicylthiazolines as ancillary ligands, which are represented as N^O. The Ir(C^N) (N^O) complexes, formed as mixtures of diastereomers, were then resolved by flash chromatography and the diastereomerically pure complexes Ir(C^N) (N^O) subjected to Suzuki cross-couplings. The post-complexation cross-couplings proceed without affecting the metal-located stereocenter and hence provide post-complexation derivatized non-racemic iridium(III) complexes, which were not easily accessible with previous methods. This strategy expands the toolbox to access functionalized non-racemic iridium(III) complexes for diverse applications in the life sciences, materials sciences, and catalysis.
报道了一种用于非对映体和对映体纯的双环金属化苯并恶唑和苯并噻唑铱(III)配合物后络合衍生化的直接方法。以[Ir(μ-Cl)(C^N)₂]表示的三氟甲磺酸酯和溴官能化铱(III)配合物二聚体，使用容易获得的手性水杨基恶唑啉和水杨基噻唑啉作为辅助配体（表示为N^O），转化为相应的非对映体配合物，以Ir(C^N)₂(N^O)表示。以非对映体混合物形式形成的Ir(C^N)₂(N^O)配合物，然后通过快速柱色谱法拆分，并且将非对映体纯的配合物Ir(C^N)₂(N^O)进行铃木交叉偶联反应。后络合交叉偶联反应在不影响金属中心立体中心的情况下进行，因此提供了后络合衍生化的非外消旋铱(III)配合物，这是以前的方法不容易获得的。该策略扩展了用于获得功能化非外消旋铱(III)配合物的工具箱，以用于生命科学、材料科学和催化等各种应用。
