skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: [NiIII(OMe)]-mediated reductive activation of CO2 affording a Ni(κ1-OCO) complex

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C5SC04652A· OSTI ID:1251399
 [1];  [1];  [2];  [3];  [3];  [1];  [4];  [5];  [5];  [1]
  1. National Tsing Hua Univ., Hsinchu (Taiwan)
  2. Chung Yuan Christian Univ., Taoyuan (Taiwan)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. National Taiwan Normal Univ., Taipei (Taiwan)
  5. National Synchrotron Radiation Research Center, Hsinchu (Taiwan)
+ Show Author Affiliations

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.

Research Organization:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1251399
Journal Information:
Chemical Science, Vol. 1021, Issue C; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

References (43)

Mononuclear Nickel(III) Complexes [Ni III (OR)(P(C 6 H 3 -3-SiMe 3 -2-S) 3 )] − (R = Me, Ph) Containing the Terminal Alkoxide Ligand: Relevance to the Nickel Site of Oxidized-Form [NiFe] Hydrogenases journal September 2008
Iron-Catalyzed Reduction of CO 2 into Methylene: Formation of C–N, C–O, and C–C Bonds journal July 2015
Phosphinite-Ni(0) Mediated Formation of a Phosphide-Ni(II)-OCOOMe Species via Uncommon Metal–Ligand Cooperation journal March 2015
Electrocatalytic CO2 Conversion to Oxalate by a Copper Complex journal January 2010
A Germanium(II) Hydride as an Effective Reagent for Hydrogermylation Reactions journal January 2009
New nickel–carbon dioxide complex: synthesis, properties, and crystallographic characterization of (carbon dioxide)-bis(tricyclohexylphosphine)nickel journal January 1975
Structure, Function, and Mechanism of the Nickel Metalloenzymes, CO Dehydrogenase, and Acetyl-CoA Synthase journal February 2014
Formation of a nickel carbon dioxide adduct and its transformation mediated by a Lewis acid journal January 2014
Fe(I)-Mediated Reductive Cleavage and Coupling of CO 2 :  An Fe II (μ-O,μ-CO)Fe II Core journal January 2007
Formation of CO 2 - Radical Ions When CO 2 is Adsorbed on Irradiated Magnesium Oxide journal July 1965
Reactions of CO 2 and CS 2 with 1,2-Bis(di- tert -butylphosphino)ethane Complexes of Nickel(0) and Nickel(I) journal November 2010
Electronic spectoscopy of isoelectronic molecules. II. Linear triatomic groupings containing sixteen valence electrons journal February 1971
Carbon Dioxide Activation at the Ni,Fe-Cluster of Anaerobic Carbon Monoxide Dehydrogenase journal November 2007
Carbon Dioxide Activation with Sterically Pressured Mid- and High-Valent Uranium Complexes journal September 2008
Mononuclear Nickel(III) and Nickel(II) Thiolate Complexes with Intramolecular S−H Proton Interacting with Both Sulfur and Nickel:  Relevance to the [NiFe]/[NiFeSe] Hydrogenases journal July 2004
How the [NiFe 4 S 4 ] Cluster of CO Dehydrogenase Activates CO 2 and NCO − journal April 2015
Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds journal January 2005
Catalysis of the electrochemical reduction of carbon dioxide journal January 2013
Oxygen-Atom Transfer from Carbon Dioxide to a Fischer Carbene at (PNP)Ir journal May 2008
Carbon Dioxide Reduction and Carbon Monoxide Activation Employing a Reactive Uranium(III) Complex journal August 2005
Utilisation of CO2 as a chemical feedstock: opportunities and challenges journal January 2007
Addition of CO 2 to Alkyl Iron Complexes, Fe(PP) 2 Me 2 journal May 2008
Differential Reduction of CO 2 by Molybdenum and Vanadium Nitrogenases journal September 2014
Discrimination of Mononuclear and Dinuclear Dinitrosyl Iron Complexes (DNICs) by S K-Edge X-ray Absorption Spectroscopy: Insight into the Electronic Structure and Reactivity of DNICs journal June 2011
Efficient Fixation of Carbon Dioxide by Hypervalent Organobismuth Oxide, Hydroxide, and Alkoxide journal August 2008
Tris(pyrazolyl)hydroboratozinc hydroxide complexes as functional models for carbonic anhydrase: on the nature of the bicarbonate intermediate journal June 1993
Carbon Dioxide Fixation by Binuclear Complexes with Hydrophobic Binding Pockets This work was supported by the Deutsche Forschungsgemeinschaft (Project No. KE 585/3-1). The author thanks Prof. Dr. H. Vahrenkamp for his support of this work. journal November 2001
Making Plastics from Carbon Dioxide:  Salen Metal Complexes as Catalysts for the Production of Polycarbonates from Epoxides and CO 2 journal June 2007
Transformation of Carbon Dioxide journal June 2007
Radical Scavenging of White Tea and Its Flavonoid Constituents by Electron Paramagnetic Resonance (EPR) Spectroscopy journal June 2014
A Linear, O-Coordinated  1-CO2 Bound to Uranium journal September 2004
The impact of Metal–Ligand Cooperation in Hydrogenation of Carbon Dioxide Catalyzed by Ruthenium PNP Pincer journal October 2013
Reactions of the Terminal Ni II −OH Group in Substitution and Electrophilic Reactions with Carbon Dioxide and Other Substrates: Structural Definition of Binding Modes in an Intramolecular Ni II ···Fe II Bridged Site journal April 2010
Mononuclear Ni(III) Complexes [Ni III (L)(P(C 6 H 3 -3-SiMe 3 -2-S) 3 )] 0/1- (L = Thiolate, Selenolate, CH 2 CN, Cl, PPh 3 ):  Relevance to the Nickel Site of [NiFe] Hydrogenases journal December 2006
Recent developments in the activation of carbon dioxide by metal complexes journal January 1999
Reversible CO 2 binding triggered by metal–ligand cooperation in a rhenium( i ) PNP pincer-type complex and the reaction with dihydrogen journal January 2014
Organosamarium-Mediated Transformations of CO 2 and COS:  Monoinsertion and Disproportionation Reactions and the Reductive Coupling of CO 2 to [O 2 CCO 2 ] 2- journal February 1998
O/C Bond Cleavage of CO 2 by Ni I journal March 2008
The Organometallic Chemistry of Carbon Dioxide journal January 1996
Efficient Fixation of Carbon Dioxide by Hypervalent Organobismuth Oxide, Hydroxide, and Alkoxide journal August 2008
Differential Reduction of CO 2 by Molybdenum and Vanadium Nitrogenases journal September 2014
Transformation of Carbon Dioxide journal September 2007
Making Plastics from Carbon Dioxide: Salen Metal Complexes as Catalysts for the Production of Polycarbonates from Epoxides and CO2 journal September 2007

Cited By (3)

Ein biomimetischer Nickelkomplex mit einem reduzierten, durch Formiatdeprotonierung erzeugten CO 2 -Liganden und sein Verhalten gegenüber CO 2 journal May 2018
A Biomimetic Nickel Complex with a Reduced CO 2 Ligand Generated by Formate Deprotonation and Its Behaviour towards CO 2 journal May 2018
XANES/EPR Evidence of the Oxidation of Nickel(II) Quinolinylpropioamide and Its Application in Csp 3 −H Functionalization journal March 2019

Linked Research (3)

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY