Facile Synthesis of Cyclometalated Ruthenium Complexes with Substituted Phenylpyridines

We have developed a new strategy that uses the Krohnke synthesis for the preparation of various substituted phenylpyridines in excellent yields (up to 88 %). Starting with the appropriate commercially available acetophenone, a variety of phenylpyridines substituted by either electron-donating (i.e. methyl, methoxy) or -withdrawing groups (i.e. bromide, nitro) on the phenyl ring are obtained in a two-step synthesis. The corresponding functionalized cyclometalated ruthenium complexes can be prepared with unusually high yields by

[1]  F. Mongin,et al.  Advances in the directed metallation of azines and diazines (pyridines, pyrimidines, pyrazines, pyridazines, quinolines, benzodiazines and carbolines). Part 1: Metallation of pyridines, quinolines and carbolines , 2001 .

[2]  H. Stoeckli-Evans,et al.  Complexes of new chiral terpyridyl ligands. Synthesis and characterization of their ruthenium(II) and rhodium(III) complexes , 1999 .

[3]  G. D. Rieck,et al.  International tables for X-ray crystallography , 1962 .

[4]  L. Vendier,et al.  Synthesis, Crystal Structure, and Second‐Order Nonlinear Optical Properties of Ruthenium( II ) Complexes with Substituted Bipyridine and Phenylpyridine Ligands , 2006 .

[5]  E. Constable,et al.  Novel synthesis of a doubly cyclometallated diruthenium complex with strongly coupled metal centres , 1993 .

[6]  Louis J. Farrugia,et al.  ORTEP-3 for Windows - a version of ORTEP-III with a Graphical User Interface (GUI) , 1997 .

[7]  J. Selbin,et al.  Study of a cyclometalated complex of ruthenium by 400-MHz two-dimensional proton NMR , 1985 .

[8]  E. Constable,et al.  Structural characterization of bis(2,2′-bipyridine) [2-(2-pyridyl)phenyl-c,n]rhodium(III) hexafluorophosphate; an analogue of a tris(2,2′-bipyridine) complex incorporating a c,n-donor ligand , 1990 .

[9]  K. R. Mann,et al.  Synthesis, spectroscopy, and electrochemical studies of binuclear tris-bipyridine ruthenium(II) complexes with oligothiophene bridges. , 2001, Inorganic chemistry.

[10]  Y. Oki,et al.  Preparations and Characterization of Cycloruthenated Complexes Derived from 1-Phenylpyrazole, 2-Phenylpyridine, and Benzo[h]quinoline , 1979 .

[11]  E. Constable,et al.  A cyclometallated analogue of tris(2,2'-bipyridine)ruthenium(II) , 1986 .

[12]  Sandrine Fraysse,et al.  Electrophilic functionalization of a cyclometallated ruthenium complex, an easy entry to new organometallic synthons , 1998 .

[13]  R. Pascal,et al.  Accelerated luminophore discovery through combinatorial synthesis. , 2004, Journal of the American Chemical Society.

[14]  E. Constable,et al.  Solvent effects in the reactions of 6-phenyl-2,2′-bipyridine with ruthenium(II) , 1993 .

[15]  R. Thouvenot,et al.  An Anionic {[MnCo(ox)3]-}n Network with Appropriate Cavities for the Enantioselective Recognition and Resolution of the Hexacoordinated Monocation [Ru(bpy)2(ppy)]+ (bpy = bipyridine, ppy = phenylpyridine) , 2001 .

[16]  Robert F. Francis,et al.  Identification of 2,5-dihydropyridine intermediates in the reactions of 2-alkyl(phenyl)-1-lithio-1,2-dihydropyridines with alkyl halides , 1978 .

[17]  F. Barigelletti,et al.  Electrochemical and Spectroscopic Properties of Cyclometallated and Non‐Cyclometallated Ruthenium(II) Complexes Containing Sterically Hindering Ligands of the Phenanthroline and Terpyridine Families , 2000 .

[18]  D. Comins,et al.  Regioselective nucleophilic addition to 3,4-lutidine , 1976 .

[19]  B. Goodall,et al.  Cyclometallation reactions : VII. Reactions of benzo[h]quinoline , 1973 .

[20]  G. Balavoine,et al.  An Effective Route to Polysubstituted Symmetric Terpyridines , 1999 .

[21]  J. Selbin,et al.  Cyclometalated complexes of ruthenium. 2. Spectral and electrochemical properties and x-ray structure of bis(2,2'-bipyridine)(4-nitro-2-(2-pyridyl)phenyl)ruthenium(II) , 1985 .

[22]  F. Barigelletti,et al.  A room temperature luminescent cyclometallated ruthenium(II) complex of 6-phenyl-2,2′-bipyridine , 1991 .

[23]  B. Malézieux,et al.  Rational Design of Three-Dimensional (3D) Optically Active Molecule-Based Magnets: Synthesis, Structure, Optical and Magnetic Properties of {[Ru(bpy)3]2+, ClO4-, [MnIICrIII(ox)3]-}n and {[Ru(bpy)2ppy]+, [MIICrIII(ox)3]-}n, with MII = MnII, NiII. X-ray Structure of {[ΔRu(bpy)3]2+, ClO4-, [ΔMnIIΔCrIII , 2001 .

[24]  Jean-Pierre Launay,et al.  Synthesis and Properties of Dinuclear Complexes with a Photochromic Bridge: An Intervalence Electron Transfer Switching “On” and “Off” , 2000 .

[25]  Louis J. Farrugia,et al.  WinGX suite for small-molecule single-crystal crystallography , 1999 .

[26]  V. Balzani,et al.  Ruthenium(II) and Osmium(II) Bis(terpyridine) Complexes in Covalently-Linked Multicomponent Systems: Synthesis, Electrochemical Behavior, Absorption Spectra, and Photochemical and Photophysical Properties , 1994 .

[27]  S. Stanforth,et al.  Catalytic cross-coupling reactions in biaryl synthesis , 1998 .

[28]  A. Lees.  Luminescence properties of organometallic complexes , 1987 .

[29]  F. Mongin,et al.  Cross-coupling reactions of phenylmagnesium halides with fluoroazines and fluorodiazines. , 2002, The Journal of organic chemistry.

[30]  Giovanni Luca Cascarano,et al.  Completion and refinement of crystal structures with SIR92 , 1993 .

[31]  S. Jung,et al.  Effect of Substitution of Methyl Groups on the Luminescence Performance of IrIII Complexes: Preparation, Structures, Electrochemistry, Photophysical Properties and Their Applications in Organic Light‐Emitting Diodes (OLEDs) , 2004 .

[32]  D. Whitten,et al.  Photochemical reactions in organized monolayer assemblies. 6. Preparation and photochemical reactivity of surfactant ruthenium(II) complexes in monolayer assemblies and at water-solid interfaces , 1977 .

[33]  J. Launay,et al.  Molecular wires built from binuclear cyclometalated complexes. , 2003, Journal of the American Chemical Society.

[34]  J. Sauvage,et al.  Construction of multicomponent systems by utilizing functionalized transition metal complexes as building blocks , 1996 .

[35]  E. V. D. Eycken,et al.  Synthesis of (E)-5-(2-arylvinyl)-2-(hetero)arylpyridines, (E)-2-(2-arylvinyl)-5-methoxycarbonylpyridines and (E, E)-2,5-bis(2-arylvinyl)pyridines as polarity and pH probes , 2002 .

[36]  V. Bonnet,et al.  Syntheses of substituted pyridines, quinolines and diazines via palladium-catalyzed cross-coupling of aryl Grignard reagents , 2002 .

[37]  Vincenzo Balzani,et al.  Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence , 1988 .

[38]  A. Lützen,et al.  Synthesis of 5‐Substituted 2,2′‐Bipyridines from Substituted 2‐Chloropyridines by a Modified Negishi Cross‐Coupling Reaction , 2002 .

[39]  F. Kröhnke.  The Specific Synthesis of Pyridines and Oligopyridines1 , 1976 .

[40]  J. Launay,et al.  A new redox site as an alternative to ferrocene to study electron transfer in self-assembled monolayers. , 2002, Chemical communications.

[41]  Sambasivarao Kotha,et al.  Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis , 2002 .

[42]  P. Gros,et al.  Straightforward access to methyl-polyheterocycles from direct para-lithiation of 3-picoline , 2001 .