Ambient stable trigonal bipyramidal copper(III) complexes equipped with an exchangeable axial ligand

Hao Ching Chang, Feng Chun Lo, Wen Chi Liu, Tsung Han Lin, Wen Feng Liaw, Ting Shen Kuo, Way-Zen Lee

Research output: Contribution to journalArticle

10 Citations (Scopus)

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 languageEnglish
Pages (from-to)5527-5533
Number of pages7
JournalInorganic Chemistry
Volume54
Issue number11
DOIs
Publication statusPublished - 2015 Jun 1

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Copper
Ligands
copper
ligands
X ray crystallography
X Ray Crystallography
Titration
Absorption spectroscopy
titration
crystallography
affinity
Chlorides
Spectrum Analysis
absorption spectroscopy
chlorides
Nuclear magnetic resonance
Electrons
Derivatives
nuclear magnetic resonance
energy

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 journalArticle

Chang, Hao Ching ; Lo, Feng Chun ; Liu, Wen Chi ; Lin, Tsung Han ; Liaw, Wen Feng ; Kuo, Ting Shen ; Lee, Way-Zen. / Ambient stable trigonal bipyramidal copper(III) complexes equipped with an exchangeable axial ligand. In: Inorganic Chemistry. 2015 ; Vol. 54, No. 11. pp. 5527-5533.
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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.",
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AU - Liu, Wen Chi

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AU - Kuo, Ting Shen

AU - Lee, Way-Zen

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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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