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Role of Axial Ligation in Gating the Reactivity of Dimethylplatinum(III) Diimine Radical Cations

Journal Article · · Organometallics
 [1];  [2];  [3];  [3];  [3];  [3];  [3];  [2]
  1. Univ. of North Carolina, Chapel Hill, NC (United States); University of North Carolina
  2. Univ. of North Carolina, Chapel Hill, NC (United States)
  3. Univ. of Virginia, Charlottesville, VA (United States)
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Electrochemical methods are coupled with chemical oxidant-based analytical strategies to evaluate the oxidative reactivity of the platinum(II) diimine complex (bpy)PtII(CH3)2 (bpy = 2,2'-bipyridine) in coordinating and non-coordinating media. Through this mechanistic analysis, we show that the one-electron oxidation of (bpy)PtII(CH3)2 generates a highly reactive, 15-electron PtIII radical cation and identify three reaction pathways that can follow this oxidation: radical–substrate dimerization, radical-radical dimerization, and oxidative disproportionation. Axial ligation of the initially generated [(bpy)PtIII(CH3)2]•+ species is a critical driver of this reactivity, gating the available mechanistic pathways and tuning the competition between radical–radical dimerization and oxidative disproportionation.
Research Organization:
Univ. of North Carolina, Chapel Hill, NC (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
SC0015303
OSTI ID:
1774201
Alternate ID(s):
OSTI ID: 1823413
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 3 Vol. 40; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (55)

Elements of Molecular and Biomolecular Electrochemistry book January 2006
Neutral and Cationic Methyl Complexes of Platinum(II) with 6-Substituted 2,2′-Bipyridines: Synthesis, Characterisation and Reactivity with Carbon Monoxide − Molecular Structures of [PtCl(methyl)(6-ethyl-2,2′-bipyridine)] and of [Pt(methyl)(acetonitrile)(6-ethyl-2,2′-bipyridine)][BF4] journal December 2000
Preparation of Dimethyl and Chloro/Methyl Complexes of Platinum(II) Supported byα-Diimine Ligands: Trends in the Ease of Oxidation to Platinum(IV) journal October 2001
Beyond Oil and Gas: The Methanol Economy journal April 2005
Increasing Catalyst Efficiency in C−H Activation Catalysis journal January 2018
Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model journal April 2003
Axiale abschirmung des quadratisch-planar konfigurierten platin(II) in strukturell charakterisiertem (bpy)PtMes2: Lumineszenz und elektrochemisch reversible Bildung von Platin(III) journal November 1992
Electronic and molecular structure of 2,2′-bipyrimidine-bridged bis(organoplatinum) complexes in various oxidation states. Radical-bridged diplatinum species and the absence of a Pt(III)/Pt(II) mixed-valent intermediate journal November 1997
On the electronic structure of oxazole journal January 1963
Direct methane conversion routes to chemicals and fuels journal August 2011
The shale gas boom in the US: Productivity shocks and price responsiveness journal August 2019
DFT study of nucleophilicity of organometallic (2,2′-bipyridine)platinum(II) complexes journal January 2015
Electrocatalytic Shilov chemistry for the oxidation of aliphatic groups journal February 2019
Dinuclear cyclometallated platinum(III) complexes. Relationship between molecular structure and crystal packing journal January 2014
Shale gas: Analysis of its role in the global energy market journal September 2014
Molecular Catalysts for Water Oxidation journal July 2015
Platinum-Catalyzed C–H Functionalization journal October 2016
Homogeneous Functionalization of Methane journal March 2017
Oxidation of Half-Lantern Pt 2 (II,II) Compounds by Halocarbons. Evidence of Dioxygen Insertion into a Pt(III)–CH 3 Bond journal July 2015
Catalytic Methane Monofunctionalization by an Electrogenerated High-Valent Pd Intermediate journal October 2017
Electrochemical Reoxidation Enables Continuous Methane-to-Methanol Catalysis with Aqueous Pt Salts journal June 2019
Methane Conversion to Syngas for Gas-to-Liquids (GTL): Is Sustainable CO 2 Reuse via Dry Methane Reforming (DMR) Cost Competitive with SMR and ATR Processes? journal August 2015
Mechanistic Aspects of C−H Activation by Pt Complexes journal June 2005
1,2-Difluorobenzene: a relatively inert and noncoordinating solvent for electrochemical studies on transition-metal complexes journal October 1989
Acetate-Bridged Platinum(III) Complexes Derived from Cisplatin journal September 2012
Synthesis and x-ray structural characterization of the first unbridged diplatinum(III) compound: bis[bis(1-imino-1-hydroxy-2,2-dimethylpropane)trichloroplatinum(III)] journal September 1991
A Combined Experimental and Density Functional Theory Investigation of Hydrocarbon Activation at a Cationic Platinum(II) Diimine Aqua Complex under Mild Conditions in a Hydroxylic Solvent journal November 2000
Kinetics and Mechanism of Methane, Methanol, and Dimethyl Ether C−H Activation with Electrophilic Platinum Complexes journal February 2006
Electrochemical Oxidation of CoCp(CO) 2 :  Radical−Substrate Reaction of a 17 e - /18 e - Pair and Production of a Unique Dimer Radical journal December 2006
Oxidation of Organoplatinum(II) by Coordinated Dimethylsulfoxide: Metal−Metal Bonded, Dinuclear, Liquid-Crystalline Complexes of Platinum(III) journal August 2010
From Hetero- to Homochiral Bis(metallahelicene)s Based on a Pt III −Pt III Bonded Scaffold: Isomerization, Structure, and Chiroptical Properties journal March 2011
Using Reduced Catalysts for Oxidation Reactions: Mechanistic Studies of the “Periana-Catalytica” System for CH 4 Oxidation journal September 2013
Binuclear Intermediates in Oxidation Reactions: [(Me 3 SiC≡C)Me 2 (bipy)Pt−PtMe 2 (bipy)] + in the Oxidation of Pt II Me 2 (bipy) (bipy = 2,2′-Bipyridine) by IPh(C≡CSiMe 3 )(OTf) (OTf = Triflate) journal May 2009
Rapid Electrochemical Methane Functionalization Involves Pd–Pd Bonded Intermediates journal November 2020
Highly Emissive Dinuclear Platinum(III) Complexes journal March 2020
Axial Shielding of 5d8 and 5d7 Metal Centers in Dimesitylplatinum Complexes with Unsaturated Chelate Ligands: Spectroscopic and Spectroelectrochemical Studies of Four Different Oxidation States journal March 1995
Oxidation of dimethylplatinum(II) complexes with alcohols: Synthesis and characterization of alkoxoplatinum(IV) complexes journal March 1984
Cationic intermediates in oxidative addition reactions of alkyl halides to d8 complexes: evidence for the SN2 mechanism journal December 1987
Reactions of Platinum(II) Complexes with Chloride-Based Oxidants: Routes to Pt(III) and Pt(IV) Products journal March 2008
Anodic Reaction of Co(η 5 -C 5 H 5 )(CO)(PPh 3 ): An Oxidatively Induced Ligand Exchange Involving a 17 e − /18 e − Redox Pair journal October 2010
Modulating Sterics in Trimethylplatinum(IV) Diimine Complexes To Achieve C–C Bond-Forming Reductive Elimination journal July 2011
Reactions of New Organoplatinum(II) and -(IV) Complexes of 1,4-Diaza-1,3-butadienes with Light and Electrons. Emission vs Photochemistry and the Electronic Structures of Ground, Reduced, Oxidized, and Low-Lying Charge-Transfer Excited States † journal January 1998
Redox Chemistry of Dimethylplatinum(II) Diimine Complexes. Oxidatively Induced Pt−Me Transfer between Transient Platinum(III) Cation Radicals journal August 1998
Ambient methane functionalization initiated by electrochemical oxidation of a vanadium (V)-oxo dimer journal July 2020
Half-lantern cyclometalated Pt( ii ) and Pt( iii ) complexes with bridging heterocyclic thiolate ligands: synthesis, structural characterization, and electrochemical and photophysical properties journal January 2019
A review on electrocatalytic oxidation of methane to oxygenates journal January 2020
Different orbital occupation by an added single electron in 1,10-phenanthroline and its 3,4,7,8-tetramethyl derivative. Evidence from electron paramagnetic resonance spectroscopy of the anion radicals and of their dimesitylplatinum( II ) complexes. X-Ray molecular structure of dimesityl(1,10-phenanthroline)platinum( II ) journal January 1995
Electrochemical and chemical oxidation of the antitumour agent [Pt{((p-HC6F4)NCH2)2}(py)2] – detection of platinum(iii) intermediates journal February 2003
A variational formulation of the polarizable continuum model journal July 2010
Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements journal October 1982
Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals journal January 1985
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative journal April 1998
An Unbridged Platinum(III) Dimer with Added Chloro Ligands in Equatorial Sites, [Pt 2 Cl 2 (phpy) 4 ] (Hphpy = phenylpyridine), Synthesized by an Oxidation with Aurous Complex journal February 2004

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Cations
Oligomers
Oxidation
Platinum
Redox reactions