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 |
|---|---|
| Pages (from-to) | 5527-5533 |
| Number of pages | 7 |
| Journal | Inorganic Chemistry |
| Volume | 54 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - 2015 Jun 1 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
Cite this
Ambient stable trigonal bipyramidal copper(III) complexes equipped with an exchangeable axial ligand. / Chang, Hao Ching; Lo, Feng Chun; Liu, Wen Chi; Lin, Tsung Han; Liaw, Wen Feng; Kuo, Ting Shen; Lee, Way-Zen.
In: Inorganic Chemistry, Vol. 54, No. 11, 01.06.2015, p. 5527-5533.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Ambient stable trigonal bipyramidal copper(III) complexes equipped with an exchangeable axial ligand
AU - Chang, Hao Ching
AU - Lo, Feng Chun
AU - Liu, Wen Chi
AU - Lin, Tsung Han
AU - Liaw, Wen Feng
AU - Kuo, Ting Shen
AU - Lee, Way-Zen
PY - 2015/6/1
Y1 - 2015/6/1
N2 - 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.
AB - 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.
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UR - http://www.scopus.com/inward/citedby.url?scp=84930674451&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.5b00603
DO - 10.1021/acs.inorgchem.5b00603
M3 - Article
AN - SCOPUS:84930674451
VL - 54
SP - 5527
EP - 5533
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 11
ER -