Fast palladium catalyzed arylation of alkenes using bulky monodentate phophorous ligands

Abstract

[EN] The new bimetallic nickel(II) compound (PPh4)4[Ni2(2)]·6H2O (3), where H8[2] stands for N,N',N'',N'''-1,2,4,5-benzene-tetrayltetrakis(oxamic acid), has been synthesized and its crystal structure determined by single-crystal X-ray diffraction. The structure of 3 consists of [Ni2(n4:n4-2)]4- anions, tetraphenylphosphonium cations, and water molecules. Facile one-electron oxidation of the square-planar diamagnetic dinickel(II) complex [Ni2(n4:n4-2)]4- generates the metallo-radical species [Ni2(n4:n4-2·+)]3- with characteristic intra-ligand ¿cation radical transitions in the visible region (475-550 nm) as well as a typical quasi-isotropic EPR signal at g ¿ 2.0.This work was supported by the CNRS (France) and the DGICYT (Spain) through project PB9421002. B. Cervera thanks the Conselleria de Educació i Ciència de la Generalitat Valenciana (Spain) for a grant.Aukauloo, A.; Ottenwaelder, X.; Ruiz, R.; Poussereau, S.; Pei, Y.; Journaux, Y.; Fleurat, P.... (1999). A Square-Planar Dinickel(II) Complex with a Noninnocent Dinucleating Oxamate Ligand: Evidence for a Ligand Radical Species. European Journal of Inorganic Chemistry. 1999(7):1067-1071. https://doi.org/10.1002/(SICI)1099-0682(199907)1999:73.0.CO;2-7S1067107119997Stubbe, J., & van der Donk, W. A. (1998). Protein Radicals in Enzyme Catalysis. Chemical Reviews, 98(2), 705-762. doi:10.1021/cr9400875Sono, M., Roach, M. P., Coulter, E. D., & Dawson, J. H. (1996). Heme-Containing Oxygenases. Chemical Reviews, 96(7), 2841-2888. doi:10.1021/cr9500500Que, L., & Ho, R. Y. N. (1996). Dioxygen Activation by Enzymes with Mononuclear Non-Heme Iron Active Sites. Chemical Reviews, 96(7), 2607-2624. doi:10.1021/cr960039fRecent reviews: [2a] , Chem. Commun. 1998, 1319–1325, and references therein.2b – , , New J. Chem. 1998, 201–210.Wang, Y. (1998). Catalytic Galactose Oxidase Models: Biomimetic Cu(II)-Phenoxyl-Radical Reactivity. Science, 279(5350), 537-540. doi:10.1126/science.279.5350.537Cox, D. D., & Que, L. (1988). Functional models for catechol 1,2-dioxygenase. The role of the iron(III) center. Journal of the American Chemical Society, 110(24), 8085-8092. doi:10.1021/ja00232a021Jang, H. G., Cox, D. D., & Que, L. (1991). A highly reactive functional model for the catechol dioxygenases. Structure and properties of [Fe(TPA)DBC]BPh4. Journal of the American Chemical Society, 113(24), 9200-9204. doi:10.1021/ja00024a028Koch, W. O., & Krüger, H.-J. (1995). Ein sehr reaktives und katalytisch wirksames Modellsystem für intradiolspaltende Catechol-Dioxygenasen: Struktur und Reaktivität von Eisen(III)-Catecholatkomplexen vonN,N′-Dimethyl-2,11-diaza[3.3](2,6)pyridinophan. Angewandte Chemie, 107(23-24), 2928-2931. doi:10.1002/ange.19951072335Inoue, K., & Iwamura, H. (1994). Ferro- and Ferrimagnetic Ordering in a Two-Dimensional Network Formed by Manganese(II) and 1,3,5-Tris[p-(N-tert-butyl-N-oxyamino)phenyl]benzene. Journal of the American Chemical Society, 116(7), 3173-3174. doi:10.1021/ja00086a077MANRIQUEZ, J. M., YEE, G. T., MCLEAN, R. S., EPSTEIN, A. J., & MILLER, J. S. (1991). A Room-Temperature Molecular/Organic-Based Magnet. Science, 252(5011), 1415-1417. doi:10.1126/science.252.5011.1415Zhang, J., Ensling, J., Ksenofontov, V., Gütlich, P., Epstein, A. J., & Miller, J. S. (1998). Molekulare Magnete mitTc-Werten über 100 K und Koerzitivfeldern bis zu 6500 Oe: Synthesen von [MII(tcne)2]⋅x CH2Cl2 (M = Mn, Fe, Co, Ni). Angewandte Chemie, 110(5), 676-679. doi:10.1002/(sici)1521-3757(19980302)110:53.0.co;2-xZhang, J., Ensling, J., Ksenofontov, V., Gütlich, P., Epstein, A. J., & Miller, J. S. (1998). [MII(tcne)2]⋅x CH2Cl2 (M=Mn, Fe, Co, Ni) Molecule-Based Magnets withTc Values Above 100 K and Coercive Fields up to 6500 Oe. Angewandte Chemie International Edition, 37(5), 657-660. doi:10.1002/(sici)1521-3773(19980316)37:53.0.co;2-lCollins, T. J., Powell, R. D., Slebodnick, C., & Uffelman, E. S. (1991). Stable highly oxidizing cobalt complexes of macrocyclic ligands. Journal of the American Chemical Society, 113(22), 8419-8425. doi:10.1021/ja00022a033Bartos, M. J., Kidwell, C., Kauffmann, K. E., Gordon-Wylie, S. W., Collins, T. J., Clark, G. C., … Weintraub, S. T. (1995). Ein stabiler Aquaeisen(III)-Komplex mitS = 1: Struktur und spektroskopische Eigenschaften. Angewandte Chemie, 107(11), 1345-1348. doi:10.1002/ange.19951071121Bartos, M. J., Kidwell, C., Kauffmann, K. E., Gordon-Wylie, S. W., Collins, T. J., Clark, G. C., … Weintraub, S. T. (1995). A Stable Aquairon(III) Complex withS= 1: Structure and Spectroscopic Properties. Angewandte Chemie International Edition in English, 34(11), 1216-1219. doi:10.1002/anie.199512161[8a] , , , , , , , , Chem. Commun. 1998, 989–990.8b – , , , , , , , , Chem. Commun. 1997, 2283–2284.Estrada, J., Fernández, I., Pedro, J., Ottenwaelder, X., Ruiz, R., & Journaux, Y. (1997). Aerobic epoxidation of olefins catalysed by square-planar cobalt(III) complexes of bis-N,N′-disubstituted oxamides and related ligands. Tetrahedron Letters, 38(13), 2377-2380. doi:10.1016/s0040-4039(97)00354-7Fernández, I., Pedro, J., Rosello, A. L., Ruiz, R., Ottenwaelder, X., & Journaux, Y. (1998). Aerobic epoxidation of olefins catalysed by square-planar nickel(II) complexes of bis- N , N ′-disubstituted oxamides and related ligands. Tetrahedron Letters, 39(18), 2869-2872. doi:10.1016/s0040-4039(98)00321-9[10a] , , , , , , J. Chem. Soc., Dalton Trans. 1997, 745–751.10b – , , , , , , , , , , , J. Chem. Soc., Dalton Trans. 1998, 781–790., , , , , , manuscript in preparation.Bossu, F. P., & Margerum, D. W. (1976). The stabilization of trivalent nickel in deprotonated-peptide complexes. Journal of the American Chemical Society, 98(13), 4003-4004. doi:10.1021/ja00429a047Bossu, F. P., Chellappa, K. L., & Margerum, D. W. (1977). Ligand effects on the thermodynamic stabilization of copper(III)-peptide complexes. Journal of the American Chemical Society, 99(7), 2195-2203. doi:10.1021/ja00449a028Fabbrizzi, L., Perotti, A., & Poggi, A. (1983). The deprotonated amido vs. the amino group in the stabilization of coordinated trivalent copper and nickel cations. An electrochemical evaluation. Inorganic Chemistry, 22(9), 1411-1412. doi:10.1021/ic00151a035Anson, F. C., Collins, T. J., Richmond, T. G., Santarsiero, B. D., Toth, J. E., & Treco, B. G. R. T. (1987). Highly stabilized copper(III) complexes. Journal of the American Chemical Society, 109(10), 2974-2979. doi:10.1021/ja00244a020Collins, T. J., Nichols, T. R., & Uffelman, E. S. (1991). A square-planar nickel(III) complex of an innocent ligand system. Journal of the American Chemical Society, 113(12), 4708-4709. doi:10.1021/ja00012a064Hanss, J., & Krüger, H.-J. (1996). Der erste stabile Kupfer(III)-Komplex mit aliphatischen Thiolaten als Liganden: struktureller und spektroskopischer Nachweis von CuII- und CuIII-Ionen in Komplexen mit quadratisch-planaren CuN2S2-Koordinationssphären. Angewandte Chemie, 108(23-24), 2989-2991. doi:10.1002/ange.19961082323Hanss, J., & Krüger, H.-J. (1996). The First Stable Copper(III) Complex Containing Aliphatic Thiolates as Ligands: Structural and Spectroscopic Evidence for CuII and CuIII Ions in Complexes with Square-Planar CuN2S2 Coordination Environments. Angewandte Chemie International Edition in English, 35(2324), 2827-2830. doi:10.1002/anie.199628271Hanss, J., & Krüger, H.-J. (1998). Erste Isolierung und strukturelle Charakterisierung eines Nickel(III)-Komplexes mit aliphatischen Thiolatdonoren. Angewandte Chemie, 110(3), 366-369. doi:10.1002/(sici)1521-3757(19980202)110:33.0.co;2-fHanss, J., & Krüger, H.-J. (1998). First Isolation and Structural Characterization of a Nickel(III) Complex Containing Aliphatic Thiolate Donors. Angewandte Chemie International Edition, 37(3), 360-363. doi:10.1002/(sici)1521-3773(19980216)37:33.0.co;2-pMichaelis, L., Schubert, M. P., & Granick, S. (1939). The Free Radicals of the Type of Wurster’s Salts. Journal of the American Chemical Society, 61(8), 1981-1992. doi:10.1021/ja01877a013Becke, A. D. (1993). Density‐functional thermochemistry. III. The role of exact exchange. The Journal of Chemical Physics, 98(7), 5648-5652. doi:10.1063/1.464913Lee, C., Yang, W., & Parr, R. G. (1988). Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Physical Review B, 37(2), 785-789. doi:10.1103/physrevb.37.785, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Gaussian 94, Revision E. 1, Gaussian, Inc., Pittsburgh, PA, 1995. In the calculations, the metal ions and the ligand have been explicitly taken into account. The PPh4+ counterions have been replaced by Na+ cations and are located at the phosphorus site of PPh4+ cations. Furthermore, the geometry used has been taken from the one determined by X-ray crystallography. We have used the 6–31G* basis set for the ligands atoms. The nickel basis set is that determined by Wachters supplemented with f-polarization function. The sodium cations have been taken as point charges (no vacant orbital on the atom), the core electrons being described by an effective core potential. This procedure, which explicitly takes into account a repulsion potential, avoids too strong orbital polarizations towards the point charges.Wachters, A. J. H. (1970). Gaussian Basis Set for Molecular Wavefunctions Containing Third‐Row Atoms. The Journal of Chemical Physics, 52(3), 1033-1036. doi:10.1063/1.1673095Gordon-Wylie, S. W., Claus, B. L., Horwitz, C. P., Leychkis, Y., Workman, J. M., Marzec, A. J., … Collins, T. J. (1998). New Magnetically Coupled Bimetallic Complexes as Potential Building Blocks for Magnetic Materials. Chemistry - A European Journal, 4(11), 2173-2181. doi:10.1002/(sici)1521-3765(19981102)4:113.0.co;2-qSurville-Barland, C., Ruiz, R., Aukauloo, A., Journaux, Y., Castro, I., Cervera, B., … Sapin˜a, F. (1998). Tuning up the Tc in Mn(II)Cu(II) bimetallic planes and design of molecular-based magnets. Inorganica Chimica Acta, 278(2), 159-169. doi:10.1016/s0020-1693(98)00016-4Ruiz, R., Surville-Barland, C., Journaux, Y., Colin, J. C., Castro, I., Cervera, B., … Sapiña, F. (1997). A Family of Oxamido-Bridged MnIICuIIBimetallic Molecular-Based Ferrimagnets:  Synthesis, EXAFS Structural Characterization, and Magnetic Properties. Chemistry of Materials, 9(1), 201-209. doi:10.1021/cm9602961SHELXL93, Program for the Refinement of Crystal Structures, University of Göttingen, DFR, 1993

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