[NiIII(OMe)]-mediated reductive activation of CO2 affording a Ni(κ1-OCO) complex
Abstract
Here, carbon dioxide is expected to be employed as an inexpensive and potential feedstock of C1 sources for the mass production of valuable chemicals and fuel. Versatile chemical transformations of CO2, i.e. insertion of CO2 producing bicarbonate/acetate/formate, cleavage of CO2 yielding μ-CO/μ-oxo transition-metal complexes, and electrocatalytic reduction of CO2 affording CO/HCOOH/CH3OH/CH4/C2H4/oxalate were well documented. Herein, we report a novel pathway for the reductive activation of CO2 by the [NiIII(OMe)(P(C6H3-3-SiMe3-2-S)3)]– complex, yielding the [NiIII(κ1-OCO˙–)(P(C6H3-3-SiMe3-2-S)3)]– complex. The formation of this unusual NiIII(κ1-OCO˙–) complex was characterized by single-crystal X-ray diffraction, EPR, IR, SQUID, Ni/S K-edge X-ray absorption spectroscopy, and Ni valence-to-core X-ray emission spectroscopy. The inertness of the analogous complexes [NiIII(SPh)], [NiII(CO)], and [NiII(N2H4)] toward CO2, in contrast, demonstrates that the ionic [NiIII(OMe)] core attracts the binding of weak σ-donor CO2 and triggers the subsequent reduction of CO2 by the nucleophilic [OMe]– in the immediate vicinity. This metal–ligand cooperative activation of CO2 may open a novel pathway promoting the subsequent incorporation of CO2 in the buildup of functionalized products.
- Authors:
-
- National Tsing Hua Univ., Hsinchu (Taiwan)
- Chung Yuan Christian Univ., Taoyuan (Taiwan)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- National Taiwan Normal Univ., Taipei (Taiwan)
- National Synchrotron Radiation Research Center, Hsinchu (Taiwan)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1251399
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Volume: 1021; Journal Issue: C; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Chiou, Tzung -Wen, Tseng, Yen -Ming, Lu, Tsai -Te, Weng, Tsu -Chien, Sokaras, Dimosthenes, Ho, Wei -Chieh, Kuo, Ting -Shen, Jang, Ling -Yun, Lee, Jyh -Fu, and Liaw, Wen -Feng. [NiIII(OMe)]-mediated reductive activation of CO2 affording a Ni(κ1-OCO) complex. United States: N. p., 2016.
Web. doi:10.1039/C5SC04652A.
Chiou, Tzung -Wen, Tseng, Yen -Ming, Lu, Tsai -Te, Weng, Tsu -Chien, Sokaras, Dimosthenes, Ho, Wei -Chieh, Kuo, Ting -Shen, Jang, Ling -Yun, Lee, Jyh -Fu, & Liaw, Wen -Feng. [NiIII(OMe)]-mediated reductive activation of CO2 affording a Ni(κ1-OCO) complex. United States. https://doi.org/10.1039/C5SC04652A
Chiou, Tzung -Wen, Tseng, Yen -Ming, Lu, Tsai -Te, Weng, Tsu -Chien, Sokaras, Dimosthenes, Ho, Wei -Chieh, Kuo, Ting -Shen, Jang, Ling -Yun, Lee, Jyh -Fu, and Liaw, Wen -Feng. Wed .
"[NiIII(OMe)]-mediated reductive activation of CO2 affording a Ni(κ1-OCO) complex". United States. https://doi.org/10.1039/C5SC04652A. https://www.osti.gov/servlets/purl/1251399.
@article{osti_1251399,
title = {[NiIII(OMe)]-mediated reductive activation of CO2 affording a Ni(κ1-OCO) complex},
author = {Chiou, Tzung -Wen and Tseng, Yen -Ming and Lu, Tsai -Te and Weng, Tsu -Chien and Sokaras, Dimosthenes and Ho, Wei -Chieh and Kuo, Ting -Shen and Jang, Ling -Yun and Lee, Jyh -Fu and Liaw, Wen -Feng},
abstractNote = {Here, carbon dioxide is expected to be employed as an inexpensive and potential feedstock of C1 sources for the mass production of valuable chemicals and fuel. Versatile chemical transformations of CO2, i.e. insertion of CO2 producing bicarbonate/acetate/formate, cleavage of CO2 yielding μ-CO/μ-oxo transition-metal complexes, and electrocatalytic reduction of CO2 affording CO/HCOOH/CH3OH/CH4/C2H4/oxalate were well documented. Herein, we report a novel pathway for the reductive activation of CO2 by the [NiIII(OMe)(P(C6H3-3-SiMe3-2-S)3)]– complex, yielding the [NiIII(κ1-OCO˙–)(P(C6H3-3-SiMe3-2-S)3)]– complex. The formation of this unusual NiIII(κ1-OCO˙–) complex was characterized by single-crystal X-ray diffraction, EPR, IR, SQUID, Ni/S K-edge X-ray absorption spectroscopy, and Ni valence-to-core X-ray emission spectroscopy. The inertness of the analogous complexes [NiIII(SPh)], [NiII(CO)], and [NiII(N2H4)] toward CO2, in contrast, demonstrates that the ionic [NiIII(OMe)] core attracts the binding of weak σ-donor CO2 and triggers the subsequent reduction of CO2 by the nucleophilic [OMe]– in the immediate vicinity. This metal–ligand cooperative activation of CO2 may open a novel pathway promoting the subsequent incorporation of CO2 in the buildup of functionalized products.},
doi = {10.1039/C5SC04652A},
journal = {Chemical Science},
number = C,
volume = 1021,
place = {United States},
year = {2016},
month = {2}
}
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