Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(II).

Covalent tethering of P(Ph)2N(C6H4C≡CH)2 ligands (P(Ph)2N(C6H4C≡CH)2 = 1,5-di-(4-ethynylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) to planar, azide-terminated glassy carbon electrode surfaces has been accomplished using a Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) coupling reaction, using a BH3←P protection-deprotection strategy. Deprotected, surface-confined ligands were metallated using [Ni(II)(MeCN)6](BF4)2. X-ray photoelectron spectroscopic measurements demonstrate that metallation introduced 1.3 equivalents Ni(II) per diphosphine onto the electrode surface. Exposure of the surface to a second diphosphine ligand, P(Ph)2N(Ph)2, resulted in the removal of Ni from the surface. Protection, coupling, deprotection, and metallation conditions were optimized using solution-phase model systems, with benzyl azide as a model for the azide-terminated carbon surface; these reactions generate a [Ni(II)(diphosphine)2](2+) complex.

[1]  Dietmar Stalke,et al.  Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination , 2015, Journal of applied crystallography.

[2]  G. Sheldrick.  Crystal structure refinement with SHELXL , 2015, Acta crystallographica. Section C, Structural chemistry.

[3]  Ling He,et al.  Unique Configuration of a Nitrogen-Doped Graphene Nanoribbon: Potential Applications to Semiconductor and Hydrogen Fuel Cell , 2014 .

[4]  B. Lotsch,et al.  Photocatalytic Hydrogen Production using Polymeric Carbon Nitride with a Hydrogenase and a Bioinspired Synthetic Ni Catalyst** , 2014, Angewandte Chemie.

[5]  M. Engelhard,et al.  A hydrogen-evolving Ni(P2N2)2 electrocatalyst covalently attached to a glassy carbon electrode: preparation, characterization, and catalysis. comparisons with the homogeneous analogue. , 2014, Inorganic chemistry.

[6]  Monte L. Helm,et al.  Production of hydrogen by electrocatalysis: making the H-H bond by combining protons and hydrides. , 2014, Chemical communications.

[7]  D. Dubois.  Development of molecular electrocatalysts for energy storage. , 2014, Inorganic chemistry.

[8]  James R. McKone,et al.  Will Solar-Driven Water-Splitting Devices See the Light of Day? , 2014 .

[9]  J. Durrant,et al.  Versatile Photocatalytic Systems for H2 Generation in Water Based on an Efficient DuBois-Type Nickel Catalyst , 2013, Journal of the American Chemical Society.

[10]  M. Engelhard,et al.  Minimal proton channel enables H2 oxidation and production with a water-soluble nickel-based catalyst. , 2013, Journal of the American Chemical Society.

[11]  James D. Blakemore,et al.  Noncovalent immobilization of electrocatalysts on carbon electrodes for fuel production. , 2013, Journal of the American Chemical Society.

[12]  M. Engelhard,et al.  The electrode as organolithium reagent: catalyst-free covalent attachment of electrochemically active species to an azide-terminated glassy carbon electrode surface. , 2013, Inorganic chemistry.

[13]  P. Kumta,et al.  Fluorine-Doped IrO2: A Potential Electrocatalyst for Water Electrolysis , 2013 .

[14]  Monte L. Helm,et al.  Production of H2 at fast rates using a nickel electrocatalyst in water-acetonitrile solutions. , 2013, Chemical communications.

[15]  D. Dubois,et al.  Two pathways for electrocatalytic oxidation of hydrogen by a nickel bis(diphosphine) complex with pendant amines in the second coordination sphere. , 2013, Journal of the American Chemical Society.

[16]  R. Bullock,et al.  Direct determination of equilibrium potentials for hydrogen oxidation/production by open circuit potential measurements in acetonitrile. , 2013, Inorganic chemistry.

[17]  I. Sharp,et al.  A Noble-Metal-Free Hydrogen Evolution Catalyst Grafted to Visible Light-Absorbing Semiconductors. , 2013, The journal of physical chemistry letters.

[18]  M. Matheron,et al.  Molecular engineering of a cobalt-based electrocatalytic nanomaterial for H₂ evolution under fully aqueous conditions. , 2013, Nature chemistry.

[19]  R. Hamers,et al.  Covalent attachment of catalyst molecules to conductive diamond: CO2 reduction using "smart" electrodes. , 2012, Journal of the American Chemical Society.

[20]  Jingguang G. Chen,et al.  A new class of electrocatalysts for hydrogen production from water electrolysis: metal monolayers supported on low-cost transition metal carbides. , 2012, Journal of the American Chemical Society.

[21]  S. Stolbov,et al.  Rational Design of Competitive Electrocatalysts for Hydrogen Fuel Cells. , 2012, The journal of physical chemistry letters.

[22]  Monte L. Helm,et al.  Studies of a series of [Ni(P(R)2N(Ph)2)2(CH3CN)]2+ complexes as electrocatalysts for H2 production: substituent variation at the phosphorus atom of the P2N2 ligand. , 2011, Inorganic chemistry.

[23]  Lee M. Bishop,et al.  Modular "click" chemistry for electrochemically and photoelectrochemically active molecular interfaces to tin oxide surfaces. , 2011, ACS applied materials & interfaces.

[24]  Daniel L DuBois,et al.  [Ni(P(Ph)2N(C6H4X)2)2]2+ complexes as electrocatalysts for H2 production: effect of substituents, acids, and water on catalytic rates. , 2011, Journal of the American Chemical Society.

[25]  Elizabeth C. Landis,et al.  Highly stable redox-active molecular layers by covalent grafting to conductive diamond. , 2011, Journal of the American Chemical Society.

[26]  Charles C. L. McCrory,et al.  Electrocatalytic O2 reduction by covalently immobilized mononuclear copper(I) complexes: evidence for a binuclear Cu2O2 intermediate. , 2011, Journal of the American Chemical Society.

[27]  R. Morris Bullock,et al.  Molecular Electrocatalysts for the Oxidation of Hydrogen and the Production of Hydrogen – The Role of Pendant Amines as Proton Relays , 2011 .

[28]  P. D. Tran,et al.  Noncovalent modification of carbon nanotubes with pyrene-functionalized nickel complexes: carbon monoxide tolerant catalysts for hydrogen evolution and uptake. , 2011, Angewandte Chemie.

[29]  D. Dubois,et al.  Comparison of Cobalt and Nickel Complexes with Sterically Demanding Cyclic Diphosphine Ligands: Electrocatalytic H2 Production by [Co(PtBu2NPh2)(CH3CN)3](BF4)2† , 2010 .

[30]  Jason E Hein,et al.  Copper-catalyzed azide-alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(I) acetylides. , 2010, Chemical Society reviews.

[31]  C. Bertozzi,et al.  Cu-free click cycloaddition reactions in chemical biology. , 2010, Chemical Society reviews.

[32]  P. D. Tran,et al.  From Hydrogenases to Noble Metal–Free Catalytic Nanomaterials for H2 Production and Uptake , 2009, Science.

[33]  Anthony L. Spek,et al.  Structure validation in chemical crystallography , 2009, Acta crystallographica. Section D, Biological crystallography.

[34]  Morten Meldal,et al.  Cu-catalyzed azide-alkyne cycloaddition. , 2008, Chemical reviews.

[35]  M. Botoshansky,et al.  Pincer click ligands. , 2008, Angewandte Chemie.

[36]  J. Reek,et al.  "Clickphine": a novel and highly versatile P,N ligand class via click chemistry. , 2006, Organic letters.

[37]  Stefan Bräse,et al.  Organic azides: an exploding diversity of a unique class of compounds. , 2005, Angewandte Chemie.

[38]  F. Himo,et al.  Copper(I)-catalyzed synthesis of azoles. DFT study predicts unprecedented reactivity and intermediates. , 2004, Journal of the American Chemical Society.

[39]  H. Birkedal,et al.  Scavenging and reclaiming phosphines associated with group 10 metal-mediated couplings. , 2004, Organic letters.

[40]  N. Devaraj,et al.  "Clicking" functionality onto electrode surfaces. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[41]  D. Briggs,et al.  Surface Analysis by Auger and X-Ray Photoelectron Spectroscopy , 2003 .

[42]  Franklin Anariba,et al.  Mono- and multilayer formation by diazonium reduction on carbon surfaces monitored with atomic force microscopy "scratching". , 2003, Analytical chemistry.

[43]  Y. Gololobov,et al.  Recent Advances in the Staudinger Reaction , 1992 .

[44]  D. R. Penn,et al.  Calculations of electron inelastic mean free paths. III. Data for 15 inorganic compounds over the 50–2000 eV range , 1991 .

[45]  D. Briggs,et al.  Practical surface analysis: By auger and x-ray photoelectron spectroscopy , 1983 .

[46]  C. Schoerner,et al.  1.5-Diaza-3.7-diphospha-cyclooctane , 1980 .

[47]  Allen J. Bard,et al.  Electrochemical Methods: Fundamentals and Applications , 1980 .

[48]  K. Dehnicke.  The Chemistry of Iodine Azide , 1979 .

[49]  N. Winograd,et al.  X-ray photoelectron spectroscopic studies of nickel-oxygen surfaces using oxygen and argon ion-bombardment , 1974 .

[50]  I. Kolthoff,et al.  Titration of bases in acetonitrile , 1967 .

[51]  J. Savéant,et al.  Potential-sweep voltammetry: General theory of chemical polarization , 1967 .

[52]  J. Savéant,et al.  Potential-sweep chronoamperometry: Kinetic currents for first-order chemical reaction parallel to electron-transfer process (catalytic currents)☆ , 1965 .

[53]  R. S. Nicholson,et al.  Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems. , 1964 .

[54]  A. Underhill,et al.  468. The preparation and properties of some bivalent transition-metal tetrafluoroborate–methyl cyanide complexes , 1962 .