The Electrochemical Behaviour of Organonickel Complexes: Mono-, Di- and Trivalent Nickel

The redox properties of organometallic nickel complexes of the type [(α-diimine)Ni(Mes)Br], [(α-diimine)Ni(Mes)2] and the complexes trans-[(PPh3)2Ni(Mes)Br] and trans-[(PPh3)2Ni(Fmes)Br] [Mes = mesityl (2,4,6-trimethylphenyl); Fmes = tris(2,4,6-trifluoromethyl)phenyl] have been studied in detail by various electrochemical and spectroelectrochemical (UV/Vis/NIR and EPR) methods. Upon electrochemical reduction, the bromido mesityl derivatives undergo cleavage of the bromide ligand. The resulting reactive species and their products from follow-up reactions are investigated. Electrochemical oxidation leads to formally trivalent nickel species. The metal contribution to the unpaired electron for the formally monovalent and trivalent nickel species can be estimated from EPR spectroscopy. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

[1]  M. Navarro,et al.  Homogeneous electro-mediated reduction of unsaturated compounds using Ni and Fe as mediators in DMF , 2006 .

[2]  E. Hey‐Hawkins,et al.  Electrochemical synthesis of the σ-aryl complex [NiBr(Mes)(bpy)] and its use as catalyst precursor for the oligomerization of ethylene (Mes = 2,4,6-trimethylphenyl, bpy = 2,2'-bipyridine) , 2006 .

[3]  Eric Léonel,et al.  Mixed effect of the supporting electrolyte and the zinc anode in the electrochemical homocoupling of 2-bromopyridines catalyzed by nickel complexes in an undivided cell. , 2005, The Journal of organic chemistry.

[4]  M. Navarro,et al.  Homogeneous electromediated reduction of the 2-cyclohexen-1-one by transition metals , 2005 .

[5]  W. Kaim,et al.  Widely Separated Reduction Processes of abpy-Coupled Areneosmium(II) Reaction Centers (abpy = 2,2'-Azobispyridine): Stabilization of the Radical Intermediate and of the Os^0Os^I^I State , 2005 .

[6]  Qing Yang,et al.  Stereospecific Electrochemical Carboxylation of β-Bromostyrene by Use of Nickel(II) Catalyst , 2005 .

[7]  J. Périchon,et al.  Nickel-catalyzed electrochemical coupling of aryl, heteroaryl or vinyl halides with activated alkyl chlorides: Synthetic and stereochemical aspects , 2004 .

[8]  W. Kaim,et al.  Complex reduction chemistry of (abpy)PtCl2, abpy = 2,2'-azobispyridine: formation of cyclic [(micro,eta2:eta1-abpy)PtCl]2(2+) with a new coordination mode for abpy and a near-infrared ligand-to-ligand intervalence charge transfer absorption of the one-electron reduced state. , 2004, Inorganic chemistry.

[9]  M. Feth,et al.  On the Electronic Structure of Mesitylnickel Complexes of α‐Diimines — Combining Structural Data, Spectroscopy and Calculations , 2004 .

[10]  J. Reilly,et al.  Alkylation of [2,2′-([2,2′-bipyridine]-6,6′-diyl)bis[phenolato]-N,N′,O,O′]nickel(II) during catalytic reduction of 1-iodooctane , 2004 .

[11]  W. Kaim,et al.  Metal vs ligand reduction in complexes of dipyrido[3,2-a:2',3'-c]phenazine and related ligands with [(C5Me5)ClM]+ (M = Rh or Ir): evidence for potential rather than orbital control in the reductive cleavage of the metal-chloride bond. , 2004, Inorganic chemistry.

[12]  A. Aukauloo,et al.  From metal to ligand electroactivity in nickel(II) oxamato complexes. , 2004, Chemical communications.

[13]  O. Sinyashin,et al.  Organonickel σ-Complexes—Key Intermediates of Electrocatalytic Cycles , 2003 .

[14]  O. Sinyashin,et al.  Kinetic features of oxidative addition of organic halides to the organonickel σ-complex , 2003 .

[15]  M. Feth,et al.  Investigation of the Ligand Exchange Behavior of Square‐Planar Nickel(II) Complexes by X‐ray Absorption Spectroscopy and X‐ray Diffraction , 2003 .

[16]  Y. Budnikova,et al.  The reactivity of 2,2"-bipyridine complexes in the electrochemical reduction of organohalides , 2002 .

[17]  Eric Léonel,et al.  Electrochemical homocoupling of 2-bromomethylpyridines catalyzed by nickel complexes. , 2002, The Journal of organic chemistry.

[18]  S. Antonczak,et al.  Intramolecular allyl transfer reaction from allyl ether to aldehyde groups: experimental and theoretical studies. , 2002, Chemistry.

[19]  S. Sengmany,et al.  Cyclopropane formation by nickel-catalysed electroreductive coupling of activated olefins and unactivated gem-dibromo compounds , 2002 .

[20]  O. Sinyashin,et al.  Highly reactive σ-organonickel complexes in electrocatalytic processes , 2001 .

[21]  A. Klein.  Synthesis, Spectroscopic Properties, and Crystal Structure of 2,2′‐Bipyridyldimesitylnickel(II) , 2001 .

[22]  J. Field,et al.  Synthesis, Structure, and Physicochemical Characterizations of a New Cationic Ruthenium(I)−Ruthenium(I) Tetracarbonyl Bipyridine Dimer Precursor for the Electrochemical Synthesis of an Organometallic Ruthenium(0) Polymer , 2001 .

[23]  T. Ziegler,et al.  DFT Studies on the Copolymerization of α-Olefins with Polar Monomers: Comonomer Binding by Nickel- and Palladium-Based Catalysts with Brookhart and Grubbs Ligands , 2001 .

[24]  A. Deronzier,et al.  A Novel Organometallic Polymer of Osmium(0), [Os(2,2′‐bipyridine)(CO)2]n: Its Electrosynthesis and Electrocatalytic Properties Towards CO2 Reduction , 2001 .

[25]  S. Mecking.  Olefin Polymerization by Late Transition Metal Complexes-A Root of Ziegler Catalysts Gains New Ground. , 2001, Angewandte Chemie.

[26]  E. Duñach,et al.  Electrochemical Reduction of Allyl Ethers in the Presence of Nickel Complexes: A Review of Synthetic Applications , 2000 .

[27]  J. Périchon,et al.  Electrosynthesis of functionalized 2-arylpyridines from functionalized aryl and pyridine halides catalyzed by nickel bromide 2,2′-bipyridine complex , 2000 .

[28]  A. Klein,et al.  Synthesis, Coordination, and Spectroscopic Properties of 2,2′‐Bipyridyldimesitylpalladium(II) and 6‐Mesityl‐2,2′‐bipyridyldimesitylpalladium(II) , 2000 .

[29]  R. Gelder,et al.  Rhodium and Iridium β-Diiminate Complexes – Olefin Hydrogenation Step by Step , 2000 .

[30]  M. Brookhart,et al.  Late-metal catalysts for ethylene homo- and copolymerization. , 2000, Chemical reviews.

[31]  C. Amatore,et al.  Anionic Pd(0) and Pd(II) intermediates in palladium-catalyzed Heck and cross-coupling reactions. , 2000, Accounts of chemical research.

[32]  J. Périchon,et al.  Electrochemical cross-coupling between functionalized aryl halides and 2-chloropyrimidine or 2-chloropyrazine catalyzed by nickel 2,2′-bipyridine complex , 2000 .

[33]  J. Périchon,et al.  Nickel-catalysed electrochemical coupling between mono- or di-chlorophenylphosphines and aryl or heteroaryl halides , 1999 .

[34]  J. Nedelec,et al.  NICKEL-BIPYRIDINE CATALYSED ELECTROSYNTHESIS OF KETONES FROM ORGANIC HALIDES AND CARBON MONOXIDE : KINETIC AND MECHANISTIC INVESTIGATIONS , 1998 .

[35]  Alan R. Brown,et al.  Structural and Voltammetric Studies on the Reduction of the Bis(2,2‘-bipyridyl)platinum(II) Cation in Aprotic Media , 1998 .

[36]  M. Marcaccio,et al.  DYNAMICS OF THE ELECTROCHEMICAL BEHAVIOR OF DIIMINE TRICARBONYL RHENIUM(I)COMPLEXES IN STRICTLY APROTIC MEDIA , 1998 .

[37]  R. Poli.  Molybdenum Open-Shell Organometallics. Spin State Changes and Pairing Energy Effects , 1997 .

[38]  A. Deronzier,et al.  Selective Synthesis and Electrochemical Behavior of trans(Cl)- and cis(Cl)-[Ru(bpy)(CO)2Cl2] Complexes (bpy = 2,2‘-Bipyridine). Comparative Studies of Their Electrocatalytic Activity toward the Reduction of Carbon Dioxide , 1997 .

[39]  W. Kaim,et al.  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 , 1997 .

[40]  R. Poli.  Open-Shell Organometallics as a Bridge between Werner-Type and Low-Valent Organometallic Complexes. The Effect of the Spin State on the Stability, Reactivity, and Structure. , 1996, Chemical reviews.

[41]  Wolfgang A. Herrmann,et al.  Applied Homogeneous Catalysis with Organometallic Compounds , 1996 .

[42]  W. Kaim,et al.  Axial Shielding of 5d8 and 5d7 Metal Centers in Dimesitylplatinum Complexes with Unsaturated Chelate Ligands: Spectroscopic and Spectroelectrochemical Studies of Four Different Oxidation States , 1995 .

[43]  M. Daněk,et al.  Simple construction of an infrared optically transparent thin-layer electrochemical cell: Applications to the redox reactions of ferrocene, Mn2(CO)10 and Mn(CO)3(3,5-di-t-butyl-catecholate)− , 1991 .

[44]  T. J. Collins,et al.  A square-planar nickel(III) complex of an innocent ligand system , 1991 .

[45]  C. Amatore,et al.  Activation of carbon dioxide by electron transfer and transition metals. Mechanism of nickel-catalyzed electrocarboxylation of aromatic halides , 1991 .

[46]  Gang. Peng,et al.  Low-potential nickel(III,II) complexes: new systems based on tetradentate amidate-thiolate ligands and the influence of ligand structure on potentials in relation to the nickel site in [NiFe]-hydrogenases , 1991 .

[47]  J. Périchon,et al.  Synthèse de biaryles dissymétriques par électroréduction d'halogénures aromatiques catalysée par des complexes du nickel associé à la 2,2′-bipyridine , 1990 .

[48]  C. Amatore,et al.  Rates and mechanism of biphenyl synthesis catalyzed by electrogenerated coordinatively unsaturated nickel complexes , 1988 .

[49]  D. M. Grove,et al.  Syntheses and characterization of unique organometallic Ni(III) aryl species: ESR and electrochemical studies and the X-Ray molecular structure of square pyramidal Ni{C6H3(CH2NMe2)2-o,o'}I2 , 1988 .

[50]  V. C. Gibson,et al.  Advances in non-metallocene olefin polymerization catalysis. , 2003, Chemical reviews.

[51]  A. Savall,et al.  Water as Solvent for Nickel‐2,2′‐Bipyridine‐Catalysed Electrosynthesis of Biaryls from Haloaryls , 2002 .

[52]  A. Deronzier,et al.  Electrosynthesis of Electroactive Metal-Metal Bonded Polymers [Ru(CO)2L]n (L = 2,2'-Bipyridine Derivatives), Their Characterization and Catalytic Activity. A Review , 2001 .

[53]  E. Duñach,et al.  Electrosynthesis of cyclic carbamates from aziridines and carbon dioxide , 2000 .

[54]  Tomoki Nagai,et al.  Synthesis and ligand substitution reactions of a homoleptic acetonitrile dipalladium(I) complex , 2000 .

[55]  E. McInnes,et al.  Electronic structure of radical anionic binuclear organoplatinum complexes. A multiple frequency EPR investigation , 1998 .

[56]  J. Périchon,et al.  Organic electroreductive coupling reactions using transition metal complexes as catalysts , 1997 .

[57]  L. Falvello,et al.  Synthesis and structural characterisation of the first homoleptic organometallic nickel(iii) compound , 1997 .

[58]  Yasuhiro Yamamoto,et al.  Dinuclear palladium(I) complexes with isocyanide and N-donor bidentate ligands , 1996 .

[59]  J. Périchon,et al.  INVESTIGATION OF THE REDUCTIVE COUPLING OF ARYL HALIDES AND/OR ETHYLCHLOROACETATE ELECTROCATALYZED BY THE PRECURSOR NIX2(BPY) WITH X-=CL-, BR- OR MESO 3- AND BPY=2,2'-DIPYRIDYL , 1996 .

[60]  W. Kaim,et al.  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-phenanthr , 1995 .

[61]  W. Kaim,et al.  A study of the reduced states of four isomeric bidiazines (diaza-2,2′-bipyridines) by UV–VIS/NIR-spectroelectrochemistry , 1992 .

[62]  W. Fawcett,et al.  Use of microelectrodes for the rapid determination of the number of electrons involved in an electrode reaction , 1985 .