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Title: Single‐Crystal to Single‐Crystal Transformations: Stepwise CO 2 Insertions into Bridging Hydrides of [(NHC)CuH] 2 Complexes

Journal Article · · Angewandte Chemie
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Institute for Integrated Catalysis Pacific Northwest National Laboratory Richland WA 99352 USA
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Abstract Mechanistic studies of substrate insertion into dimeric [(NHC)CuH] 2 (NHC=N‐heterocyclic carbene) complexes with two bridging hydrides have been shown to require dimer dissociation to generate transient, highly reactive (NHC)Cu−H monomers in solution. Using single‐crystal to single‐crystal (SC‐SC) transformations, we discovered a new pathway of stepwise insertion of CO 2 into [(NHC)CuH] 2 without complete dissociation of the dimer. The first CO 2 insertion into dimeric [(IPr*OMe)CuH] 2 (IPr*OMe=N,N′‐bis(2,6‐bis(diphenylmethyl)‐4‐methoxy‐phenyl)imidazole‐2‐ylidene) produced a dicopper formate hydride [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐H). A second CO 2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐1,1‐O 2 CH), containing two different bonding modes of the bridging formate. These dicopper formate complexes are inaccessible from solution reactions since the dicopper core cleanly ruptures to monomeric complexes when dissolved in a solvent.

Sponsoring Organization:
USDOE
OSTI ID:
1985197
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 30 Vol. 135; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (67)

Hydrogenation of Carbon Dioxide to Formate Catalyzed by a Copper/1,8-Diazabicyclo[5.4.0]undec-7-ene System journal April 2015
Double Single-Crystal-to-Single-Crystal Transformation and Small-Molecule Activation in Rhodium NHC Complexes journal July 2011
Consecutive Molecular Crystalline-State Reactions with Metal Complexes journal October 2011
Molecular Zinc Dihydride Stabilized by N-Heterocyclic Carbenes journal March 2013
Bonding and Reactivity of a μ-Hydrido Dicopper Cation journal October 2013
Heterogeneous Catalysis of CO 2 Conversion to Methanol on Copper Surfaces journal October 2014
An Air- and Water-Tolerant Zinc Hydride Cluster That Reacts Selectively With CO2 journal April 2015
Selective Reduction of CO 2 to a Formate Equivalent with Heterobimetallic Gold- - -Copper Hydride Complexes journal October 2017
Heterolysis of Dihydrogen by Nucleophilic Calcium Alkyls journal October 2018
Facially Dispersed Polyhydride Cu 9 and Cu 16 Clusters Comprising Apex‐Truncated Supertetrahedral and Square‐Face‐Capped Cuboctahedral Copper Frameworks journal February 2020
Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity journal March 2020
Chemical Batteries with CO 2 journal December 2021
Molecular Zinc Hydride Cations [ZnH] + : Synthesis, Structure, and CO 2 Hydrosilylation Catalysis journal October 2020
Synthesis of a Boron–Imidazolate Framework Nanosheet with Dimer Copper Units for CO 2 Electroreduction to Ethylene journal June 2021
Facile Insertion of Carbon Dioxide into Cu 2 (μ-H) Dinuclear Units Supported by Tetraphosphine Ligands journal September 2014
Highly Active and Selective Catalysis of Copper Diphosphine Complexes for the Transformation of Carbon Dioxide into Silyl Formate journal June 2013
Synthesis and Characterization of a Cu 14 Hydride Cluster Supported by Neutral Donor Ligands journal February 2015
A Fluxional Cu 8 H 6 Cluster Supported by Bis(diphenylphosphino)methane and its Facile Reaction with CO 2 journal May 2017
Carbon Dioxide Insertion into Bridging Iron Hydrides: Kinetic and Mechanistic Studies: Carbon Dioxide Insertion into Bridging Iron Hydrides: Kinetic and Mechanistic Studies journal February 2019
Metal(II) Formates (M = Fe, Co, Ni, and Cu) Stabilized by Tetramethylethylenediamine (tmeda): Convenient Molecular Precursors for the Synthesis of Supported Nanoparticles journal March 2019
Organometallic chemistry in the solid state journal December 1998
Reaction of olefins and dienes with binuclear rhodium hydride complexes to generate bridging alkenyl, dienyl and diene units journal January 1988
Recent advances in the homogeneous hydrogenation of carbon dioxide journal December 2004
Progress and Perspectives of Electrochemical CO 2 Reduction on Copper in Aqueous Electrolyte journal April 2019
Copper(I) Complexes Containing PCP Ligand Catalyzed Hydrogenation of Carbon Dioxide to Formate under Ambient Conditions journal March 2021
Hexanuclear Copper(I) Hydride from the Reduction-Induced Decarboxylation of a Dicopper(II) Formate journal September 2020
Heterolytic Scission of Hydrogen Within a Crystalline Frustrated Lewis Pair journal October 2020
Access to Metal Centers and Fluxional Hydride Coordination Integral for CO2 Insertion into [Fe3(μ-H)3]3+ Clusters journal April 2021
Ultrahigh Size Exclusion Selectivity for Carbon Dioxide from Nitrogen/Methane in an Ultramicroporous Metal–Organic Framework journal May 2022
Gas-Phase Reactions of Carbon Dioxide with Copper Hydride Anions Cu 2 H 2 – : Temperature-Dependent Transformation journal July 2018
Light-Assisted Catalytic Hydrogenation of Carbon Dioxide at a Low Pressure by a Dinuclear Iridium Polyhydride Complex journal January 2021
Synthesis and Reactivity of New Copper(I) Hydride Dimers journal February 2016
Calcium Hydride Insertion Reactions with Unsaturated C–C Bonds journal December 2018
A Molecular Copper Catalyst for Hydrogenation of CO 2 to Formate journal August 2015
Side Arm Twist on Zn-Catalyzed Hydrosilylative Reduction of CO 2 to Formate and Methanol Equivalents with High Selectivity and Activity journal April 2018
Catalysis Research of Relevance to Carbon Management:  Progress, Challenges, and Opportunities journal April 2001
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation journal June 2013
Catalysis for the Valorization of Exhaust Carbon: from CO 2 to Chemicals, Materials, and Fuels. Technological Use of CO 2 journal November 2013
Molecular solid-state organometallic chemistry of tripodal (polyphosphine)metal complexes. Catalytic hydrogenation of ethylene at iridium journal March 1993
Self assembly and dioxygen reactivity of an asymmetric, triply bridged diiron(II) complex with imidazole ligands and an open coordination site journal October 1989
The Reactivity Patterns of Low-Coordinate Iron−Hydride Complexes journal May 2008
CO 2 Hydrogenation to Formate and Formic Acid by Bimetallic Palladium–Copper Hydride Clusters journal April 2020
Reactivity of Hydride Bridges in High-Spin [3M–3(μ-H)] Clusters (M = Fe II , Co II ) journal August 2015
Triphosphine-Ligated Copper Hydrides for CO 2 Hydrogenation: Structure, Reactivity, and Thermodynamic Studies journal August 2016
Direct Characterization of a Reactive Lattice-Confined Ru 2 Nitride by Photocrystallography journal February 2017
Lattice-Hydride Mechanism in Electrocatalytic CO 2 Reduction by Structurally Precise Copper-Hydride Nanoclusters journal July 2017
Fundamental processes at polynuclear centers. Kinetic analysis of the reaction of a carbon-nitrogen double bond with the [Rh2(.mu.-H)2] core of binuclear rhodium hydrides journal September 1988
Reactions of binuclear rhodium hydrides with imines: factors influencing the insertion of carbon-nitrogen double bonds into rhodium-hydride bonds journal April 1990
Copper-Catalyzed Hydroboration of Carbon Dioxide journal April 2013
Photochemical Reaction of Diruthenium Tetrahydride-Bridged Complexes with Carbon Dioxide: Insertion of CO 2 into a Ru–H Bond versus C═O Double-Bond Cleavage journal August 2014
Ligand exchanges and selective catalytic hydrogenation in molecular single crystals journal June 2010
Operando studies reveal active Cu nanograins for CO2 electroreduction journal February 2023
Tandem copper hydride–Lewis pair catalysed reduction of carbon dioxide into formate with dihydrogen journal October 2018
Copper complexes as catalyst precursors in the electrochemical hydrogen evolution reaction journal January 2016
Magnesium hydride alkene insertion and catalytic hydrosilylation journal January 2019
Cu( i ) complex bearing a PNP-pincer-type phosphaalkene ligand with a bulky fused-ring Eind group: properties and applications to FLP-type bond activation and catalytic CO 2 reduction journal January 2020
In crystallo organometallic chemistry journal January 2021
Accelerating the insertion reactions of (NHC)Cu–H via remote ligand functionalization journal January 2021
Reactions of a β-diketiminate zinc hydride complex with heterocumulenes journal January 2010
Highly efficient catalytic hydrosilylation of carbon dioxide by an N-heterocyclic carbene copper catalyst journal January 2013
N-Heterocyclic carbene (NHC)–copper-catalysed transformations of carbon dioxide journal January 2013
Infrared multiple photon dissociation spectroscopy of anionic copper formate clusters journal November 2020
Organometallic synthesis, reactivity and catalysis in the solid state using well-defined single-site species
  • Pike, Sebastian D.; Weller, Andrew S.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 373, Issue 2037 https://doi.org/10.1098/rsta.2014.0187
journal March 2015
Synthesis and Characterization of a Rhodium(I)  -Alkane Complex in the Solid State journal August 2012
Organocalcium-mediated nucleophilic alkylation of benzene journal December 2017
Reactions of nitriles with binuclear rhodium hydrides. The stepwise reduction of a carbon–nitrogen triple bond at two metal centres journal September 1992
Amidines as Effective Ancillary Ligands in Copper-catalyzed Hydrogenation of Carbon Dioxide journal March 2020

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