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Bis(imino)pyridine iron complexes for catalytic carbene transfer reactions.

ABSTRACT: The bis(imino)pyridine iron complex, for the first time, is developed as an effective metal carbene catalyst for carbene transfer reactions of donor-acceptor diazo compounds. Its broad catalytic capability is demonstrated by a range of metal carbene reactions, from cyclopropanation, cyclopropenation, epoxidation, and Doyle-Kirmse reaction to O-H insertion, N-H insertion, and C-H insertion reactions. The asymmetric cyclopropanation of styrene and methyl phenyldiazoacetate was successfully achieved by the new chiral bis(imino)pyridine iron catalyst, which delivers a new gateway for the development of chiral iron catalysis for metal carbene reactions.

SUBMITTER: Wang B

PROVIDER: S-EPMC6839806 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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Bis(imino)pyridine iron complexes for catalytic carbene transfer reactions.

Wang Ban B Howard Isaac G IG Pope Jackson W JW Conte Eric D ED Deng Yongming Y

Chemical science 20190702 34

The bis(imino)pyridine iron complex, for the first time, is developed as an effective metal carbene catalyst for carbene transfer reactions of donor-acceptor diazo compounds. Its broad catalytic capability is demonstrated by a range of metal carbene reactions, from cyclopropanation, cyclopropenation, epoxidation, and Doyle-Kirmse reaction to O-H insertion, N-H insertion, and C-H insertion reactions. The asymmetric cyclopropanation of styrene and methyl phenyldiazoacetate was successfully achieve ...[more]

PMID: 31853351

Similar Datasets

O2 activation by bis(imino)pyridine iron(II)-thiolate complexes.

Project description:The new iron(II)-thiolate complexes [((iPr)BIP)Fe(II)(SPh)(Cl)] (1) and [((iPr)BIP)Fe(II)(SPh)(OTf)] (2) [BIP = bis(imino)pyridine] were prepared as models for cysteine dioxygenase (CDO), which converts Cys to Cys-SO(2)H at a (His)(3)Fe(II) center. Reaction of 1 and 2 with O(2) leads to Fe-oxygenation and S-oxygenation, respectively. For 1 + O(2), the spectroscopic and reactivity data, including (18)O isotope studies, are consistent with an assignment of an iron(IV)-oxo complex, [((iPr)BIP)Fe(IV)(O)(Cl)](+) (3), as the product of oxygenation. In contrast, 2 + O(2) results in direct S-oxygenation to give a sulfonato product, PhSO(3)(-). The positioning of the thiolate ligand in 1 versus 2 appears to play a critical role in determining the outcome of O(2) activation. The thiolate ligands in 1 and 2 are essential for O(2) reactivity and exhibit an important influence over the Fe(III)/Fe(II) redox potential.

| S-EPMC3224977 | biostudies-literature

Pyridine(diimine) Iron Diene Complexes Relevant to Catalytic [2+2]-Cycloaddition Reactions.

Project description:The synthesis, characterization, and catalytic activity of pyridine(diimine) iron piperylene and isoprene complexes are described. These diene complexes are competent precatalysts for (i) the selective cross-[2+2]-cycloaddition of butadiene or (E)-piperylene with ethylene and α-olefins and (ii) the 1,4-hydrovinylation of isoprene with ethylene. In the former case, kinetic analysis implicates the diamagnetic η4-piperylene complex as the resting state prior to rate-determining oxidative cyclization. Variable temperature 1H NMR and EXSY experiments established that diene exchange from the diamagnetic, 18e- complexes occurs rapidly in solution at ambient temperature through a dissociative mechanism. The solid-state structure of (Me(Et)PDI)Fe(η4-piperylene) (Me(Et)PDI = 2,6-(2,6-Me2-C6H3N═CEt)2C5H3N), was determined by single-crystal X-ray diffraction and confirmed the s-trans coordination of the monosubstituted 1,3-diene. Possible relationships between ligand-controlled diene coordination geometry, metallacycle denticity, and chemoselectivity of iron-mediated cycloaddition reactions are discussed.

| S-EPMC7236768 | biostudies-literature

Mechanism of the Bis(imino)pyridine-Iron-Catalyzed Hydromagnesiation of Styrene Derivatives.

Project description:Iron-catalyzed hydromagnesiation of styrene derivatives offers a rapid and efficient method to generate benzylic Grignard reagents, which can be applied in a range of transformations to provide products of formal hydrofunctionalization. While iron-catalyzed methodologies exist for the hydromagnesiation of terminal alkenes, internal alkynes, and styrene derivatives, the underlying mechanisms of catalysis remain largely undefined. To address this issue and determine the divergent reactivity from established cross-coupling and hydrofunctionalization reactions, a detailed study of the bis(imino)pyridine iron-catalyzed hydromagnesiation of styrene derivatives is reported. Using a combination of kinetic analysis, deuterium labeling, and reactivity studies as well as in situ 57Fe Mössbauer spectroscopy, key mechanistic features and species were established. A formally iron(0) ate complex [ iPrBIPFe(Et)(CH2═CH2)]- was identified as the principle resting state of the catalyst. Dissociation of ethene forms the catalytically active species which can reversibly coordinate the styrene derivative and mediate a direct and reversible β-hydride transfer, negating the necessity of a discrete iron hydride intermediate. Finally, displacement of the tridentate bis(imino)pyridine ligand over the course of the reaction results in the formation of a tris-styrene-coordinated iron(0) complex, which is also a competent catalyst for hydromagnesiation.

| S-EPMC6686191 | biostudies-literature

Copper(I) complexes of mesoionic carbene: structural characterization and catalytic hydrosilylation reactions.

Project description:Two series of different Cu(I)-complexes of "click" derived mesoionic carbenes are reported. Halide complexes of the type (MIC)CuI (with MIC = 1,4-(2,6-diisopropyl)-phenyl-3-methyl-1,2,3-triazol-5-ylidene (for 1b), 1-benzyl-3-methyl-4-phenyl-1,2,3-triazol-5-ylidene (for 1c)) and cationic complexes of the general formula [Cu(MIC)2]X (with MIC =1,4-dimesityl-3-methyl-1,2,3-triazol-5-ylidene, X = CuI2- (for 2á), 1,4-dimesityl-3-methyl-1,2,3-triazol-5-ylidene, X = BF4- (for 2a), 1,4-(2,6-diisopropyl)phenyl-3-methyl-1,2,3-triazol-5-ylidene, X = BF4- (for 2b), 1-benzyl-3-methyl-4-phenyl-1,2,3-triazol-5-ylidene, X = BF4- (for 2c)) have been prepared from CuI or [Cu(CH3CN)4](BF4) and the corresponding ligands, respectively. All complexes were characterized by elemental analysis and standard spectroscopic methods. Complexes 2á and 1b were studied by single-crystal X-ray diffraction analysis. Structural analysis revealed 2á to adopt a cationic form as [Cu(MIC)2](CuI2) and comparison of the NMR spectra of 2á and 2a confirmed this conformation in solution. In contrast, after crystallization complex 1b was found to adopt the desired neutral form. All complexes were tested for the reduction of cyclohexanone under hydrosilylation condition at elevated temperatures. These complexes were found to be efficient catalysts for this reaction. 2c was also found to catalyze this reaction at room temperature. Mechanistic studies have been carried out as well.

| S-EPMC6272443 | biostudies-literature

Catalytic Activity of <i>trans</i>-Bis(pyridine)gold Complexes.

Project description:Gold catalysis has become one of the fastest growing fields in chemistry, providing new organic transformations and offering excellent chemoselectivities under mild reaction conditions. Methodological developments have been driven by wide applicability in the synthesis of complex structures, whereas the mechanistic understanding of Au(III)-mediated processes remains scanty and have become the Achilles' heel of methodology development. Herein, the systematic investigation of the reactivity of bis(pyridine)-ligated Au(III) complexes is presented, based on NMR spectroscopic, X-ray crystallographic, and DFT data. The electron density of pyridines modulates the catalytic activity of Au(III) complexes in propargyl ester cyclopropanation of styrene. To avoid strain induced by a ligand with a nonoptimal nitrogen-nitrogen distance, bidentate bis(pyridine)-Au(III) complexes convert into dimers. For the first time, bis(pyridine)Au(I) complexes are shown to be catalytically active, with their reactivity being modulated by strain.

| S-EPMC7343288 | biostudies-literature

Transfer Hydrogenation of Ketones Catalyzed by Symmetric Imino-N-heterocyclic Carbene Co(III) Complexes.

Project description:The synthesis of new moisture-sensitive imine-functionalized N-heterocyclic carbene (NHC) precursor salts [1-(2-[(hydroxyl-benzylidene)-amino]-ethyl)-3-R-3H-imidazole-1-ium bromide; R = methyl (1a), ethyl (1b), and benzyl (1c)] is reported. Subsequent deprotonation of 1a-c and coordination of the in situ generated NHC ligands to CoBr2 led to the isolation of air-stable six-coordinate Co(III) complexes 2a-c, respectively. All the salts and complexes were fully characterized. Single-crystal X-ray analysis of 2a and 2c showed octahedral Co centers hexacoordinated to two NHC carbons, two imine nitrogen atoms, and two phenolate oxygens in the form [C^N^O(Co3+)C^N^O]. The complexes were used in the catalytic transfer hydrogenation (CTH) of a range of ketones in 2-propanol as the solvent and hydrogen donor. Based on a low catalyst concentration of 0.4 mol %, significant conversions in the range of 70-99% were recorded at high turnover frequencies up to 1635 h-1. A mechanism to account for the steps involved in the CTH of cyclohexanone by complex 2a is proposed and supported by data from cyclic voltammetry, low-resolution mass spectrometry, UV, and IR spectroscopic techniques.

| S-EPMC7033672 | biostudies-literature

Fischer Carbene Complexes of Iridium(I) for Application in Catalytic Transfer Hydrogenation.

Project description:New examples of the very rare class of iridium(I) Fischer carbene complexes (FCCs) are reported from the facile transmetalation from group 6 FCCs. Postcomplexation modification of either the carbene ligand or the ancillary coligands results in a tunable IrI metal center, for unprecedented application as a (pre)catalyst in a benchmark transfer hydrogenation reaction. The introduction of an aminocarbene ligand with a pendant N-donor moiety capable of hemilabile coordination yielded the best catalytic results with turnover frequencies reaching 445 h-1 and requiring 0.1 mol % catalyst and 0.5 mol % base loading, respectively.

| S-EPMC7311058 | biostudies-literature

Electronic Structure Determination of Pyridine N-Heterocyclic Carbene Iron Dinitrogen Complexes and Neutral Ligand Derivatives.

Project description:The electronic structures of pyridine N-heterocyclic dicarbene (iPrCNC) iron complexes have been studied by a combination of spectroscopic and computational methods. The goal of these studies was to determine if this chelate engages in radical chemistry in reduced base metal compounds. The iron dinitrogen example (iPrCNC)Fe(N2)2 and the related pyridine derivative (iPrCNC)Fe(DMAP)(N2) were studied by NMR, Mössbauer, and X-ray absorption spectroscopy and are best described as redox non-innocent compounds with the iPrCNC chelate functioning as a classical ? acceptor and the iron being viewed as a hybrid between low-spin Fe(0) and Fe(II) oxidation states. This electronic description has been supported by spectroscopic data and DFT calculations. Addition of N,N-diallyl-tert-butylamine to (iPrCNC)Fe(N2)2 yielded the corresponding iron diene complex. Elucidation of the electronic structure again revealed the CNC chelate acting as a ? acceptor with no evidence for ligand-centered radicals. This ground state is in contrast with the case for the analogous bis(imino)pyridine iron complexes and may account for the lack of catalytic [2? + 2?] cycloaddition reactivity.

| S-EPMC4195514 | biostudies-literature

Synthesis and ligand non-innocence of thiolate-ligated (N4S) Iron(II) and nickel(II) bis(imino)pyridine complexes.

Project description:The known iron(II) complex [Fe(II)(LN3S)(OTf)] (1) was used as starting material to prepare the new biomimetic (N4S(thiolate)) iron(II) complexes [Fe(II)(LN3S)(py)](OTf) (2) and [Fe(II)(LN3S)(DMAP)](OTf) (3), where LN3S is a tetradentate bis(imino)pyridine (BIP) derivative with a covalently tethered phenylthiolate donor. These complexes were characterized by X-ray crystallography, ultraviolet-visible (UV-vis) spectroscopic analysis, (1)H nuclear magnetic resonance (NMR), and Mössbauer spectroscopy, as well as electrochemistry. A nickel(II) analogue, [Ni(II)(LN3S)](BF4) (5), was also synthesized and characterized by structural and spectroscopic methods. Cyclic voltammetric studies showed 1-3 and 5 undergo a single reduction process with E(1/2) between -0.9 V to -1.2 V versus Fc(+)/Fc. Treatment of 3 with 0.5% Na/Hg amalgam gave the monoreduced complex [Fe(LN3S)(DMAP)](0) (4), which was characterized by X-ray crystallography, UV-vis spectroscopic analysis, electron paramagnetic resonance (EPR) spectroscopy (g = [2.155, 2.057, 2.038]), and Mössbauer (? = 0.33 mm s(-1); ?E(Q) = 2.04 mm s(-1)) spectroscopy. Computational methods (DFT) were employed to model complexes 3-5. The combined experimental and computational studies show that 1-3 are 5-coordinate, high-spin (S = 2) Fe(II) complexes, whereas 4 is best described as a 5-coordinate, intermediate-spin (S = 1) Fe(II) complex antiferromagnetically coupled to a ligand radical. This unique electronic configuration leads to an overall doublet spin (S(total) = 1/2) ground state. Complexes 2 and 3 are shown to react with O2 to give S-oxygenated products, as previously reported for 1. In contrast, the monoreduced 4 appears to react with O2 to give a mixture of sulfur oxygenates and iron oxygenates. The nickel(II) complex 5 does not react with O2, and even when the monoreduced nickel complex is produced, it appears to undergo only outer-sphere oxidation with O2.

| S-EPMC3827697 | biostudies-other

Oxidative addition of carbon-carbon bonds with a redox-active bis(imino)pyridine iron complex.

Project description:Addition of biphenylene to the bis(imino)pyridine iron dinitrogen complexes, ((iPr)PDI)Fe(N(2))(2) and [((Me)PDI)Fe(N(2))](2)(?(2)-N(2)) ((R)PDI = 2,6-(2,6-R(2)-C(6)H(3)-N?CMe)(2)C(5)H(3)N; R = Me, (i)Pr), resulted in oxidative addition of a C-C bond at ambient temperature to yield the corresponding iron biphenyl compounds, ((R)PDI)Fe(biphenyl). The molecular structures of the resulting bis(imino)pyridine iron metallacycles were established by X-ray diffraction and revealed idealized square pyramidal geometries. The electronic structures of the compounds were studied by Mössbauer spectroscopy, NMR spectroscopy, magnetochemistry, and X-ray absorption and X-ray emission spectroscopies. The experimental data, in combination with broken-symmetry density functional theory calculations, established spin crossover (low to intermediate spin) ferric compounds antiferromagnetically coupled to bis(imino)pyridine radical anions. Thus, the overall oxidation reaction involves cooperative electron loss from both the iron center and the redox-active bis(imino)pyridine ligand.

| S-EPMC3777725 | biostudies-literature

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