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Abstract: This work reports the synthesis and catalytic properties of new mono- and bidentate palladium(0)-[60]fullerene complexes, prepared by reaction of alpha-keto stabilized phosphorus ylides [Ph2P(CH2)nPPh2=C(H)C(O)C6H4-p-R] (n = 1, R = Ph, NO2, (Y1, Y2); n = 2, R = Ph, NO2, (Y3, Y4)), C60 and Pd(dba)2 (dibenzylideneacetone (dba)). Two coordination modes were observed: bidentate P,C-coordinated in the case of [(eta ?C60)Pd(kappa2 ?Y1)] (1) and [(eta2?C60)Pd(kappa2?Y2)] (2) and monodentate P-coordinated for [(eta2?C60)Pd(Y3)2] (3) and [(eta2?C60)Pd(Y4)2] (4) complexes. All complexes have been fully characterized by 1H, 13C and 31P NMR spectroscopic methods and other conventional techniques such as IR, thermogravimetry, inductively coupled plasma optical emission spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy and transmission electron microscopy analysis. Also, the catalytic activity of [60]fullerene-based nanocatalyst 2 in homo- and heterogeneous Mizoroki?Heck coupling reactions of various aryl chlorides with styrene was evaluated. The results implied that the both reactions exhibit their beneficial aspects such as high activity for homogeneous catalysis and facile separation and reusability for heterogeneous one. Furthermore, DFT studies of geometry-optimized monodentate and bidentate structures for 1 and 3 were calculated at the BP86/LANL2DZ and B3LYP/LANL2MB levels of theory to understand the origin of the observed coordination modes. Graphical Abstract: [Figure not available: see fulltext.].

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Asymmetric dearomative [3 + 2] cycloaddition reactions of 3-nitroindoles with vinyl aziridine and vinyl cyclopropanes have been respectively successfully developed in the presence of a chiral box/Pd(0) complex. A series of enantiomerically enriched 3a-nitro-hexahydropyrrolo[2,3-b]indole and 8b-nitrohexahydrocyclopenta[b]indole derivatives containing three contiguous chiral centers are smoothly obtained in high yields with satisfactory regio-, chemo-, and enantioselectivity. Remarkably, the synthetic utility of this process was demonstrated through direct reductive amination and functionalization of the carbon-carbon double bond of the desired products.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The reaction of the oxocyclobutenyl palladium(II) complex 2 with terminal alkyne 3 in the presence of CuI or with organozincs yielded differently 2,3-disubstituted cyclobutenones 4 or 5 via the stoichiometric Sonogashira- or Negishi-type reactions, respectively. In addition, the possibility of the synthesis of cyclobutenones 4 from 1, CO, and 3 catalyzed by the Pd complex was also demonstrated.

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Chapter 1 An introduction to palladium catalysis,
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The aryl palladium complexes [PdI(C6H4CH2OH-2)(N^N)] (N^N = bpy = 2,2?-bipyridyl (1a), tbbpy = 4,4?-di-tert-butyl-2,2?-bipyridine (1b), tmeda = N,N,N?,N?-tetramethylethylenediamine (1c)) were synthesized by oxidative addition of 2-iodobenzyl alcohol to one equivalent of “[Pd(dba)2]” (dba = dibenzylideneacetone) in the presence of the N N ligands. By reaction of 1a with three equivalents of XyNC (Xy = 2,6-dimethylphenyl) the insertion complex trans-[PdI{C(-NXy)(C6H4CH2OH-2)}(CNXy)2] (2) was formed. The reaction of 1a with KOtBu resulted in the formation of the chelate complex [Pd(kappa2-C,O-C6H4CH2O-2)(bpy)] (3), which crystallizes as pairs of molecules bridged by hydrogen bonds to water of crystallization. Complex 3 reacts with XyNC, forming the cyclic imidate N-(2,6-dimethylphenyl)-2-benzofuran-1(3H)-imine (4). By reaction of 3 with various primary alkyl halides RCH2X, the complexes [PdX(C6H4CH2OCH2R-2)(bpy)] (X = I, R = H (5a), X = Br, R = Ph (5b), p-C6H4CH2Br (5c), p-C6H4Br (5d), and p-C6H4I (5e)) were obtained. When the reaction of 3 with p-C6H4(CH2Br)2 was carried out in a 2:1 ratio, the dinuclear arylpalladium complex [{(bpy)BrPd(C6H4CH2OCH2-2)}2(C6H4-1,4)] (6) formed. An halide exchange reaction on 5e, using AgOTf and an excess of NaI, afforded [PdI{C6H4(CH2OCH2(C6H4I-4))-2}(bpy)] (5f), which by oxidative addition to [Pd(dba)2] in the presence of bpy formed another dinuclear arylpalladium complex, [(bpy)IPd(C6H4CH2-2)O(CH2C6H4-4)PdI(bpy)] (7). All the complexes have been extensively characterized by NMR spectroscopy. The crystal structures of 1a, 3·H2O, and 5e were determined by X-ray diffraction studies.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Oxidative addition of Co(COMe)(CO)4 and MoMeCp(CO)3 to Pd(dba)2 (dba = dibenzylideneacetone) in the presence of the bidentate ligand L2 (L2 = dppe (1,2-bis(diphenylphosphino)ethane), tmeda (N,N,N?,N?-tetramethylethylenediamine), bpy (2,2?-bipyridine), phen (1,10-phenanthroline)) takes place to give L2(MeCO)Pd-Co(CO)4 (L2 = dppe (1), tmeda (2), bpy (3), phen (4)) and (dppe)MePd-MoCp(CO)3 (5), respectively.

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The ferrocene-functionalised anilines 2,6-Pr2i-4-Fc-C6H2NH2 (3a), 2,6-Pr2i-4-Fc-C6H2N(SiMe 3)2 (3b), 2,6-Pr2i-4-Fc-C?C-C6H2NH 2 (5a) and 2,6-Pr2i-4-Fc-C?C-C6H 2N(SiMe3)2 (5b) (Fc=ferrocenyl) have been prepared by Pd-catalysed cross-coupling reactions. The crystal structure of 5b has been determined. The NSi2 plane and the aryl ring plane form a dihedral angle of 89.8 . The N atom is trigonal planar [C-N distance 1.459(4) A]. The Cp ring and the aryl ring planes, which are connected by the C?C spacer, form a dihedral angle of 85.8 . 3a and 5a have been utilised for the preparation of the novel redox-functionalised imido complexes [Mo(N-2,6-Pr2i-4-Fc-C6H2) 2Cl2(DME)] (6) and [Mo(N-2,6-Pr2i-4-Fc-C?C-C6H 2)2Cl2(DME)] (7) (DME=1,2-dimethoxyethane). Electrochemical investigations by cyclic voltammetry revealed a pronounced interaction between the respective N functional group and the ferrocenyl moiety for all six compounds, which is largest for 6. Elsevier Science Ltd.

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An enantiospecific palladium-catalyzed decarboxylative coupling of acyclic beta,gamma-alkynoic acids with various aryl iodides to chiral tetrasubstituted allenes is described. The coupling reaction comprises a decarboxylative gamma-palladation of alpha,alpha-disubstituted carboxylic acids to provide the tetrasubstituted allenes with complete point-to-axial chirality transfer in excellent yields.

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The coordination chemistry of the new bidentate nitrogen ligands 8-(2-pyridyl)quinoline (8-PQ) and 8-(6-methyl-2-pyridyl)quinoline) (Me-8-PQ) towards palladium and platinum has been studied. Several (N?N)Pd(R)Cl and (N?N)Pd(alkene) complexes have been synthesised. The complex (8-PQ)Pd(Me)Cl has been characterised by a single crystal X-ray determination (crystal data: triclinic space group P 1 with a=8.513(5), b=9.338(4), c=10.219(2) A, alpha=108.11(2), beta=89.82(3), gamma=116.81(4), V=680.1(6) A3, R=0.033, Z=2). A fast CO insertion occurs into the palladium-carbon bond of the complexes (N?N)Pd(Me)Cl providing the (N?N)Pd(C(O)Me)Cl complexes. For (8-PQ)Pd(C(O)Me)Cl an X-ray structure determination has been carried out (crystal data: monoclinic space group P21/c with a=9.084(4), b=10.179(3), c=16.400(3) A, beta=95.59(2), V=1509.2(9) A3, R=0.043, Z=4). Unexpected in both molecular structures is the large dihedral angle between the plane of the bidentate nitrogen ligand and the coordination plane of the palladium. Both bidentate coordinating ligands 8-PQ and Me-8-PQ show a relatively large bite angle. A monodentate coordination mode has been observed for the complexes (N?N)M(PEt3)Cl2 (M=Pd, Pt), as the pyridyl group of the ligand is coordinated to the metal while the quinoline group is dissociated from the metal, which is shown in the X-ray structure determination for the complex (8-PQ)Pd(PEt3)Cl2 (crystal data: monoclinic space group P21/a with a=15.736(2), b=7.782(1), c=18.255(3) A, beta=102.98(1), V=2178.3(6) A3, R=0.062, Z=4).

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Reference:
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5-Carbapterocarpens, one of them displaying estrogenic activity, were prepared from alpha-aryltetralones in high yields through a one-pot, BBr3-promoted O-demethylation and cyclization sequence. The key alpha-aryltetralone intermediates were obtained by direct alpha-arylation of tetralones with o-alkoxybromoarenes in the presence of Pd2(dba)3 (2.5 mol-%) and tBu3PHBF4 (10 mol-%) as catalysts, together with 2.5 equiv. of KOH in dioxane/H2O (4:1), under microwave irradiation conditions (80 W, 100 C, 40 min), leading to alpha-monoaryltetralones in good yields.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method