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Title: An Adaptable N‐Heterocyclic Carbene Macrocycle Hosting Copper in Three Oxidation States

Journal Article · · Angewandte Chemie
ORCiD logo [1]; ORCiD logo [1];  [1];  [2];  [1];  [1];  [3];  [2]; ORCiD logo [1]
  1. Institute of Inorganic Chemistry University of Göttingen Tammannstrasse 4 37077 Göttingen Germany
  2. Department of Inorganic Spectroscopy Max Planck Institute for Chemical Energy Conversion Stiftstrasse 34–36 45470 Mülheim an der Ruhr Germany
  3. Department of Chemistry &, Catalysis Research Center Technische Universität München Lichtenbergstrasse 4 85748 Garching bei München Germany
+ Show Author Affiliations

Abstract A neutral hybrid macrocycle with two trans ‐positioned N‐heterocyclic carbenes (NHCs) and two pyridine donors hosts copper in three oxidation states (+I–+III) in a series of structurally characterized complexes ( 1 – 3 ). Redox interconversion of [LCu] +/2+/3+ is electrochemically (quasi)reversible and occurs at moderate potentials ( E 1/2 =−0.45 V and +0.82 V (vs. Fc/Fc + )). A linear C NHC ‐Cu‐C NHC arrangement and hemilability of the two pyridine donors allows the ligand to adapt to the different stereoelectronic and coordination requirements of Cu I versus Cu II /Cu III . Analytical methods such as NMR, UV/Vis, IR, electron paramagnetic resonance, and Cu Kβ high‐energy‐resolution fluorescence detection X‐ray absorption spectroscopies, as well as DFT calculations, give insight into the geometric and electronic structures of the complexes. The XAS signatures of 1 – 3 are textbook examples for Cu I , Cu II , and Cu III species. Facile 2‐electron interconversion combined with the exposure of two basic pyridine N sites in the reduced Cu I form suggest that [LCu] +/2+/3+ may operate in catalysis via coupled 2 e − /2 H + transfer.

Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1594199
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 14 Vol. 132; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (91)

Ein paramagnetischer Kupfer(III)-Komplex mit oktaedrischem CuIIIS6-Koordinationspolyeder journal February 1999
A Paramagnetic Copper(III) Complex Containing an Octahedral CuIIIS6 Coordination Polyhedron journal February 1999
Warum denn Kupfer? – Strukturen und Reaktionsmechanismen von Organocupratclustern in der Organischen Chemie journal November 2000
Aryl CbH Activation by CuII To Form an Organometallic Aryl–CuIII Species: A Novel Twist on Copper Disproportionation This research was supported by MICYT of Spain through project PBQ2000-0548 and with the grant SGR-3102-UG-01 as well as the Distinction award from from CIRIT Generalitat de Catalunya (Spain). An FI doctoral grant from CIRIT to X.R. and financial support from the National Institutes of Health (USA; T.D.P.S. GM-50730; K.O.H. RR-01209) are also acknowledged. SSRL operations are funded by the Department of Energy, Basic Energy Sciences, and the SSRL Structural Molecular Biology Program is supported by the NIH NCRR BTP and the DOE OBER. journal August 2002
Wherefore Art Thou Copper? Structures and Reaction Mechanisms of Organocuprate Clusters in Organic Chemistry journal November 2000
Aryl CbH Activation by CuII To Form an Organometallic Aryl–CuIII Species: A Novel Twist on Copper Disproportionation This research was supported by MICYT of Spain through project PBQ2000-0548 and with the grant SGR-3102-UG-01 as well as the Distinction award from from CIRIT Generalitat de Catalunya (Spain). An FI doctoral grant from CIRIT to X.R. and financial support from the National Institutes of Health (USA; T.D.P.S. GM-50730; K.O.H. RR-01209) are also acknowledged. SSRL operations are funded by the Department of Energy, Basic Energy Sciences, and the SSRL Structural Molecular Biology Program is supported by the NIH NCRR BTP and the DOE OBER. journal August 2002
Synthese und Struktur überraschend stabiler Tetrakis(trifluormethyl)cuprat(III)-Salze journal October 1993
Die Vermeidung der Oxidationsstufe CuIII im Komplex [CuI(CF3)4]− durch Oxidation einer Trifluormethylgruppe journal January 1995
Diamagnetic–Paramagnetic Conversion of Tris(2-pyridylthio)methylcopper(III) through a Structural Change from Trigonal Bipyramidal to Octahedral journal November 2006
Homoleptic Crown N-Heterocyclic Carbene Complexes journal August 2007
Heterocyclische Carbene – Synthese und Koordinationschemie journal April 2008
Direct Synthesis of Iron, Cobalt, Nickel, and Copper Complexes of N-Heterocyclic Carbenes by Using Commercially Available Metal Powders journal July 2009
A 6,11,16-Triarylbiphenylcorrole with an adj -CCNN Core: Stabilization of an Organocopper(III) Complex journal July 2015
Experimentelle und theoretische Untersuchung der Existenz von Cu II , Cu III und Cu IV in Kupfercorrolen journal September 2015
Synthesis and Structure of Surprisingly Stable Tetrakis(trifluoromethyl)cuprate(III) Salts journal October 1993
Elusiveness of CuIII Complexation; Preference for Trifluoromethyl Oxidation in the Formation of[CuI(CF3)4]− Salts journal January 1995
Diamagnetic–Paramagnetic Conversion of Tris(2-pyridylthio)methylcopper(III) through a Structural Change from Trigonal Bipyramidal to Octahedral journal November 2006
Homoleptic Crown N-Heterocyclic Carbene Complexes journal August 2007
Heterocyclic Carbenes: Synthesis and Coordination Chemistry journal April 2008
Direct Synthesis of Iron, Cobalt, Nickel, and Copper Complexes of N-Heterocyclic Carbenes by Using Commercially Available Metal Powders journal July 2009
A 6,11,16-Triarylbiphenylcorrole with an adj -CCNN Core: Stabilization of an Organocopper(III) Complex journal July 2015
Experimental and Theoretical Investigations of the Existence of Cu II , Cu III , and Cu IV in Copper Corrolato Complexes journal September 2015
Synthesis and Characterization of [Cu(NHC) 2 ]X Complexes: Catalytic and Mechanistic Studies of Hydrosilylation Reactions journal November 2007
Mechanistic Insights into the Oxidative Coupling of N-Heterocyclic Carbenes within the Coordination Sphere of Copper Complexes journal August 2014
Electronic Structures and Reactivities of Corrole−Copper Complexes journal April 2004
High-valent copper in biomimetic and biological oxidations journal December 2016
High-valent transition metal centers and noninnocent ligands in metalloporphyrins and related molecules: a broad overview based on quantum chemical calculations journal September 2001
The electronic properties and stereochemistry of mono-nuclear complexes of the copper(II) ion journal July 1970
Synthesis and structural characterization of a [Ag4]4+ cluster stabilized by a mixed-donor N-heterocyclic carbene linked cyclophane and the first reported synthesis of a N-heterocyclic carbene complex in water journal April 2003
Copper–NHC complexes in catalysis journal June 2015
Multidentate N -heterocyclic carbene complexes of the 3d metals: Synthesis, structure, reactivity and catalysis journal June 2017
Two 2D grid-based Co(II) amino acid Schiff base complexes with left- and right-handed helical chains: Structures and magnetism journal July 2014
Copper(II) complexes of a heterotopic N- heterocyclic carbene ligand: Preparation and catalytic application journal March 2018
Sonogashira-type cross-coupling reactions catalyzed by copper complexes of pincer N-heterocyclic carbenes journal April 2018
1D coordination polymers of silver(I) and copper(II) based on bis(N-heterocyclic carbene) ligands: Synthesis and structural studies journal July 2010
Seven Clues to Ligand Noninnocence: The Metallocorrole Paradigm journal March 2019
Electronic Structure of Corrole Derivatives: Insights from Molecular Structures, Spectroscopy, Electrochemistry, and Quantum Chemical Calculations journal November 2016
Copper–Oxygen Complexes Revisited: Structures, Spectroscopy, and Reactivity journal January 2017
Smart N-Heterocyclic Carbene Ligands in Catalysis journal February 2017
High-Oxidation-State 3d Metal (Ti–Cu) Complexes with N -Heterocyclic Carbene Ligation journal March 2018
N-Heterocyclic Carbene Complexes of Copper, Nickel, and Cobalt journal January 2019
Cu(I) Complexes of Pincer Pyridine-Based N-Heterocyclic Carbenes with Small Wingtip Substituents: Synthesis and Structural and Spectroscopic Studies journal November 2016
Mechanistic Elucidation of the Arylation of Non-Spectator N -Heterocyclic Carbenes at Copper Using a Combined Experimental and Computational Approach journal July 2015
Iron Complexes of a Macrocyclic N-Heterocyclic Carbene/Pyridine Hybrid Ligand journal May 2015
Direct Synthesis of a Copper(II) N-Heterocyclic Carbene Complex in Air journal August 2017
Aerobic Copper-Catalyzed Organic Reactions journal June 2013
Copper Active Sites in Biology journal January 2014
Coinage Metal− N -Heterocyclic Carbene Complexes journal August 2009
Chemical Redox Agents for Organometallic Chemistry journal January 1996
First-Row Transition Metal Complexes of the Strongly Donating Pentadentate Ligand PY4Im journal December 2010
Copper(II) and Copper(III) Complexes of Pyrrole-Appended Oxacarbaporphyrin journal August 2007
X-ray absorption edge determination of the oxidation state and coordination number of copper. Application to the type 3 site in Rhus vernicifera laccase and its reaction with oxygen journal October 1987
Trans Doubly N-Confused Porphyrins:  Cu(III) Complexation and Formation of Rodlike Hydrogen-Bonding Networks journal December 2003
Bidentate NHC-Based Chiral Ligands for Efficient Cu-Catalyzed Enantioselective Allylic Alkylations:  Structure and Activity of an Air-Stable Chiral Cu Complex journal September 2004
Direct Synthesis of High-Valent Aryl–Cu(II) and Aryl–Cu(III) Compounds: Mechanistic Insight into Arene C–H Bond Metalation journal April 2014
Doubly N-Confused Porphyrin:  A New Complexing Agent Capable of Stabilizing Higher Oxidation States journal February 2000
A Systematic K-edge X-ray Absorption Spectroscopic Study of Cu(III) Sites journal June 2000
Electronic Structure of Gallium, Copper, and Nickel Complexes of Corrole. High-Valent Transition Metal Centers versus Noninnocent Ligands journal May 2000
Spectroscopic Evidence for a 3d 10 Ground State Electronic Configuration and Ligand Field Inversion in [Cu(CF 3 ) 4 ] 1– journal February 2016
Hetero Cu(III)–Pd(II) Complex of a Dibenzo[ g , p ]chrysene-Fused Bis-dicarbacorrole with Stable Organic Radical Character journal October 2017
Ground-State Copper(III) Stabilized by N-Confused/N-Linked Corroles: Synthesis, Characterization, and Redox Reactivity journal April 2018
Homoleptic carbene-silver(I) and carbene-copper(I) complexes journal September 1993
Synthesis and Structural Characterization of an Imidazolium-Linked Cyclophane and the Silver Complex of an N-Heterocyclic Carbene-Linked Cyclophane journal April 2001
Synthesis and Characterization of a Saddle-Shaped Nickel−Carbene Complex Derived from an Imidazolium-Linked m eta -Cyclophane journal June 2002
Cationic Copper(I) Complexes as Efficient Precatalysts for the Hydrosilylation of Carbonyl Compounds journal April 2006
Copper(II) Hydroxide Complexes of N-Heterocyclic Carbenes and Catalytic Oxidative Amination of Arylboronic Acids journal March 2010
Unexpected C carbene −X (X: I, Br, Cl) Reductive Elimination from N-Heterocyclic Carbene Copper Halide Complexes Under Oxidative Conditions journal September 2010
Synthesis and Characterization of Novel Iron(II) Complexes with Tetradentate Bis(N-heterocyclic carbene)–Bis(pyridine) (NCCN) Ligands journal January 2012
Remarkable Stability of Copper(II)–N-Heterocyclic Carbene Complexes Void of an Anionic Tether journal April 2014
High-valent organometallic copper and palladium in catalysis journal April 2012
An overview of N-heterocyclic carbenes journal June 2014
Dinuclear gold( i ) complexes of bridging bidentate carbene ligands: synthesis, structure and spectroscopic characterisation journal January 2004
Structural variation in copper( i ) complexes with pyridylmethylamide ligands: structural analysis with a new four-coordinate geometry index, τ 4 journal January 2007
Simple synthesis of neutral and cationic Cu-NHC complexes journal January 2015
Re-evaluating the Cu K pre-edge XAS transition in complexes with covalent metal–ligand interactions journal January 2015
Theoretical rationalisation for the mechanism of N-heterocyclic carbene-halide reductive elimination at Cu III , Ag III and Au III journal January 2016
Well-defined coinage metal transfer agents for the synthesis of NHC-based nickel, rhodium and palladium macrocycles journal January 2016
Stable Au III complexes with four N-heterocyclic carbene groups can be prepared in high yield directly from KAuCl 4 journal January 2017
A bench stable formal Cu( iii ) N -heterocyclic carbene accessible from simple copper( ii ) acetate journal January 2018
Asymmetric lithium(i) and copper(ii) alkoxy-N-heterocyclic carbene complexes; crystallographic characterisation and Lewis acid catalysisElectronic supplementary information (ESI) available: full synthetic and structural details. See http://www.rsc.org/suppdata/cc/b4/b404614e/ journal January 2004
Structure and reactivity of a new anionic N-heterocyclic carbene silver(i) complex journal January 2005
A new alternative to Stryker's reagent in hydrosilylation: synthesis, structure, and reactivity of a well-defined carbene–copper(ii) acetate complex journal January 2005
Room-temperature aerobic formation of a stable aryl–Cu(iii) complex and its reactions with nucleophiles: highly efficient and diverse arene C–H functionalizations of azacalix[1]arene[3]pyridine journal January 2009
Simple and versatile selective synthesis of neutral and cationic copper(i) N-heterocyclic carbene complexes using an electrochemical procedure journal January 2012
Exploiting a dimeric silver transmetallating reagent to synthesize macrocyclic tetracarbene complexes journal January 2012
Isolation of a potassium bis(1,2,3-triazol-5-ylidene)carbazolide: a stabilizing pincer ligand for reactive late transition metal complexes journal January 2014
The role of organometallic copper(iii) complexes in homogeneous catalysis journal January 2013
Cu(III)-Mediated Aerobic Oxidations journal December 2018
The Cambridge Structural Database
  • Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179 https://doi.org/10.1107/S2052520616003954
journal April 2016
Structure and spectroscopic properties of the dimeric copper(I) N-heterocyclic carbene complex [Cu 2 (CNC t -Bu ) 2 ](PF 6 ) 2 journal July 2015
Recent Development of Functionalized N-heterocyclic Carbene Ligands:Coordination Chemistry and Catalytic Applications journal November 2007

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