Ambient Stable Trigonal Bipyramidal Copper(III) Complexes Equipped with an Exchangeable Axial Ligand

作者：Chang Hao Ching; Lo Feng Chun; Liu Wen Chi; Lin Tsung Han; Liaw Wen Feng; Kuo Ting Shen; Lee Way Zen

来源：Inorganic Chemistry, 2015, 54(11): 5527-5533.

DOI：10.1021/acs.inorgchem.5b00603

A stable trigonal bipyramidal copper(III) complex, [PPN] [Cu((TMS)PS3)Cl] (1, wherein PPN represents bis(triphenylphosphine)iminium), was synthesized from CuCl2/PPNCl via intramolecular copper(II) disproportionation. Under ambient conditions, the axial chloride of 1 is exchangeable in solution thus making 1 serve as art intermediate to prepare trigonal bipyramidal copper(III) derivatives, e.g., [PPN][Cu((TMS)PS3)(N-3)] (2) and [Cu((TMS)PS3)(DABCO)] (3). Diamagnetic complexes 1-3 were fully characterized by X-ray crystallography, NMR, UV-vis, and Cu K-edge absorption spectroscopy. A series of UV-vis titrations were performed to investigate the relative ligand affinity toward the [Cu((TMS)PS3)] moiety, verifying the 1:1 binding equilibrium between various ligands. Compared to known copper(III) compounds, Cu K-edge absorptions of 1-3 possess lower pre-edge energy and higher shakedown transition energy, which, respectively, attribute to the electron donation from (TMS)PS3(3-) ligand and their trigonal ligand field.

• 出版日期2015-6-1
• 单位清华大学