Straube Axel, Coburger Peter, Michak Marvin, Ringenberg Mark R, Hey-Hawkins Evamarie
Institute of Inorganic Chemistry, Universität Leipzig, Johannisallee 29, D-04103 Leipzig, Germany.
Dalton Trans. 2020 Dec 8;49(46):16667-16682. doi: 10.1039/d0dt02743j.
Changing the aromatic core of C3-symmetric tris(ferrocenyl)arene-based tris-phosphanes has profound effects on their coordination behaviour towards gold(i). Depending on the arene (s-triazine, benzene, or trifluorobenzene), four different coordination modes can be distinguished and their preference has been rationalised using computational methods. The corresponding 1 : 1 ligand-to-metal complexes, studied by variable-temperature NMR spectroscopy, revealed fluctional behaviour in solution. Given the presence of up to three or six ferrocenylene spacers per complex, their electrochemistry was investigated. The redox-responsive nature of the complexes can be advantageously exploited in the catalytic ring-closing isomerisation of N-(2-propyn-1-yl)benzamide, where the benzene-based 2 : 3 ligand-to-metal complex has been shown to display multiple activity states depending on the degree of (reversible) oxidation in a preliminary trial.
改变基于C3对称三（二茂铁基）芳烃的三膦的芳香核，对它们与金（I）的配位行为有深远影响。根据芳烃（均三嗪、苯或三氟苯）的不同，可以区分出四种不同的配位模式，并且已使用计算方法对它们的偏好进行了合理化解释。通过变温核磁共振光谱研究的相应1:1配体-金属配合物，在溶液中显示出波动行为。鉴于每个配合物中存在多达三个或六个二茂铁撑间隔基，对它们的电化学性质进行了研究。这些配合物的氧化还原响应性质可有利地用于N-（2-丙炔-1-基）苯甲酰胺的催化闭环异构化反应中，在初步试验中，基于苯的2:3配体-金属配合物已显示出根据（可逆）氧化程度呈现多种活性状态。
