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Use of an electron-reservoir complex together with air to generate N-heterocyclic carbenes

Imidazolium salts with suitable substituents are readily deprotonated to stable NHC carbenes using the electron-reservoir complex [FeICp(eta6-C6Me6)], 1, in the presence of air (via a superoxide radical anion acting as a base). Less stable NHC carbenes can be conveniently obtained from imidazolium salts using the neutral base [FeIICp(eta5-C6Me5CH2)] obtained from 1 and air. Copyright

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Multidentate N-heterocyclic carbene complexes of the 3d metals: Synthesis, structure, reactivity and catalysis

N-Heterocyclic carbene (NHC) ligands are attracting worldwide interest because of their considerable scope and potential in coordination/organometallic chemistry, catalysis and materials science and this is reflected by the exponential growth in the number of relevant publications. The focus of this review is on the synthesis, structures and reactivity of 3d metals complexes with bis-NHC, tripodal NHC and tetrapodal NHC ligands. These metals are particularly relevant because of their generally lower cost and availability. The literature coverage includes the year 2015. This review is organized in six major sections, five of them are dedicated to each of the families of NHC ligands covered (chelating NHC, bridging NHC, chelating and bridging NHC, tripodal NHC and tetrapodal NHC ligands). Each section is in turn divided into subparts, one for each 3d metal. The seventh section is concerned with the catalytic applications, and we first examine C?H and C?C bond formation, the latter including polymerization, oligomerization and cross coupling reactions (Suzuki, Heck?). This is followed by C?N, C?O, C?B, C?Si, C?S and C?Br bond formation reactions. Reduction reactions and the conversion of sugars into 5-hydroxymethylfurfural are also discussed. After the Conclusion, a paragraph provides an update of the most recent articles that appeared in the literature after completion of the review.

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Copper(I) heteroleptic bis(NHC) and mixed NHC/phosphine complexes: Syntheses and catalytic activities in the one-pot sequential CuAAC reaction of aromatic amines

A series of 2-coordinate heteroleptic Cu(I) complexes of the general formula [Cu(IPr)(L)]PF6 (2-5, L = NHC or phosphine) have been synthesized via either (i) chlorido substitution by phosphine or in situ generated free NHC or (ii) the Ag-NHC transfer protocol using [CuCl(IPr)] (1) as a precursor (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene). The reactions of precursor 1 with diphosphine ligands afforded 3-coordinate heteroleptic Cu(I) complexes of the type [Cu(IPr)(L2)]PF6 (6 and 7, L2 = diphosphine). Complexes 1-7 have been subjected to a catalytic one-pot sequential CuAAC study, in which aromatic amines serve as the precursors to aryl azides. Hetero-bis(NHC) complexes 2-4 proved to be generally superior compared to their mixed NHC/phosphine counterparts 5-7. Overall, complex [Cu(Bn2-imy)(IPr)]PF6 (2), bearing the Bn 2-imy (Bn2-imy = 1,3-dibenzyl-imidazolin-2-ylidene) coligand, showed the best catalytic performance.

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Azaborines: Synthesis and use in the generation of stabilized boron-substituted carbocations

A formal N-heterocyclic carbene insertion into the B-H bond of 9-BBN followed by a ring expansion reaction is reported. NHC-9-BBN adducts were reacted in one or two steps to give the corresponding di- or triazaborines. Hydride abstraction of selected species with [Ph3C]+ is facile, giving rise to 6pi-aromatic cations with Lewis acidity comparable to Lewis acids commonly employed in frustrated Lewis pairs.

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NHC-Pd(II)-azole complexes catalyzed Suzuki?Miyaura cross-coupling of sterically hindered aryl chlorides with arylboronic acids

In order to synthesize hindered biaryls efficiently, a series of NHC-Pd(II)-azole complexes bearing sterically hindered ligands were synthesized and characterized. The steric environment effect as well as the electronic effect of the azole ligands has been assessed. All these complexes were applied in the Suzuki?Miyaura cross-coupling reaction of sterically hindered aryl chlorides with low catalysts loadings (0.1 mol %) under mild conditions in air and good to excellent isolated yields of sterically hindered biaryls were obtained.

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Complexes: Synthesis, characterization and catalytic activities in reduction reactions and Click Chemistry. on the advantage of using well-defined catalytic systems

The preparation of three series of [(NHC)CuX] complexes (NHC = N-heterocyclic carbene, X = Cl, Br, or I) is reported. These syntheses are high yielding and only use readily available starting materials. The prepared complexes were spectroscopically and structurally characterized. Notably, two of them present a bridging NHC ligand between two copper centers in the solid state, an extremely rare coordination mode for these ligands. These complexes were then applied to two distinct organic reactions: the hydrosilylation of ketones and the 1,3-dipolar cycloaddition of azides and alkynes. In both transformations, outstanding catalytic systems were found for preparing the corresponding products in excellent yields and short reaction times. Most remarkably, the screening of well-defined systems in the hydrosilylation reaction allowed for the identification of a pre-catalyst previously overlooked since, originally, catalytic species were in situ generated. Under such conditions, major formation of [(NHC)2Cu]+ species, inactive in this reduction reaction, occurred instead of the expected copper hydride. These results highlight one of the most important advantages of employing well-defined complexes in catalysis: gaining an improved control of the nature of the catalytically relevant species in the reaction media.

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METHOD OF PREPARING METAL COMPLEXES OF FORMULA Z-M, IN PARTICULAR CARBENE-METAL COMPLEXES

The present invention relates to an improved method of preparing metal complexes, in particular carbene-metal complexes. The method comprises the step of subjecting a salt of formula Z+-X- and a non-ionic metal salt of formula MLn or subjecting a metallate of formula Z+?MLnX- to a mechanical mixing process in the presence of a base. The method allows to formation of heterocyclic carbene? metal complexes such as a nitrogen-containing heterocyclic carbene (NHC)?metal complexes. The invention also relates to the use of metal complexes, in particular carbene-metal complexes such as heterocyclic carbene-metal complexes obtainable by the method according to the present invention as catalysts.

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A direct and practical approach for the synthesis of Au(I)-NHC complexes from commercially available imidazolium salts and Au(III) salts

A direct and practical approach for the synthesis of Au(I)-NHC complexes from imidazolium salts and commercially available aurate salt (MAuCl 4¡¤2H2O) is described. The reaction proceeded without sacrificing carbene transfer agent (Ag2O) or using highly sensitive free NHC.

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Robust Buchwald-Hartwig amination enabled by ball-milling

An operationally simple mechanochemical method for the Pd catalysed Buchwald-Hartwig amination of arylhalides with secondary amines has been developed using a Pd PEPPSI catalyst system. The system is demonstrated on 30 substrates and applied in the context of a target synthesis. Furthermore, the performance of the reaction under aerobic conditions has been probed under traditional solution and mechanochemical conditions, the observations are discussed herein.

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 250285-32-6, Name is 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride, molecular formula is C27H37ClN2. In a Patent£¬once mentioned of 250285-32-6, Application In Synthesis of 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride

Coupling of formaldehyde to glycoaldehyde using N-heterocyclic carbene catalysts

Glycoaldehyde (GA) is prepared via self condensation of formaldehyde in the presence of a n-heterocyclic carbene to generate GA and glyceraldehyde (GlyAld) with selectivity toward forming the GA. The carbene is generated in situ by the addition of a base to the salt form of the catalyst. Selectivity is controlled by tuning the active site of the catalyst, either sterically and/or electronically.

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