Abstract
A stable trigonal bipyramidal copper(III) complex, [PPN][Cu(TMSPS3)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 an intermediate to prepare trigonal bipyramidal copper(III) derivatives, e.g., [PPN][Cu(TMSPS3)(N3)] (2) and [Cu(TMSPS3)(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(TMSPS3)] 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 TMSPS33- ligand and their trigonal ligand field.
Original language | English |
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Pages (from-to) | 5527-5533 |
Number of pages | 7 |
Journal | Inorganic Chemistry |
Volume | 54 |
Issue number | 11 |
DOIs | |
Publication status | Published - 2015 Jun 1 |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
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CCDC 1049179: Experimental Crystal Structure Determination
Chang, H. (Creator), Lo, F. (Creator), Liu, W. (Creator), Lin, T. (Creator), Liaw, W. (Creator), Kuo, T. (Creator) & Lee, W. (Creator), Unknown Publisher, 2016
DOI: 10.5517/ccdc.csd.cc146rhl, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc146rhl&sid=DataCite
Dataset
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CCDC 1049181: Experimental Crystal Structure Determination
Chang, H. (Creator), Lo, F. (Creator), Liu, W. (Creator), Lin, T. (Creator), Liaw, W. (Creator), Kuo, T. (Creator) & Lee, W. (Creator), Unknown Publisher, 2016
DOI: 10.5517/ccdc.csd.cc146rkn, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc146rkn&sid=DataCite
Dataset
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CCDC 1049180: Experimental Crystal Structure Determination
Chang, H. (Creator), Lo, F. (Creator), Liu, W. (Creator), Lin, T. (Creator), Liaw, W. (Creator), Kuo, T. (Creator) & Lee, W. (Creator), Unknown Publisher, 2016
DOI: 10.5517/ccdc.csd.cc146rjm, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc146rjm&sid=DataCite
Dataset