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Rhodium(I) complexes were explored as catalysts for the hydrogen borrowing reactions of amines and alcohols. Bidentate carbene-triazole ligands were readily synthesized via "click" reactions which allowed a diversity of ligand backbones to be accessed. The catalytic transformations are highly efficient, able to reach completion in under 6 h, and promote C-N bond formation across a range of primary alcohol and amine substrates. Moreover, site-selective catalysis can be achieved using substrates with more than one reactive site. A rhodium(I) complex covalently attached to a carbon black surface was also deployed in the hydrogen borrowing coupling reaction of aniline with benzyl alcohol. This represents the first report of a heterogeneous rhodium catalyst used for hydrogen borrowing.
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A gold(III) complex of an N-heterocyclic carbene based hemilabile ligand with two pendant pyrazole arms (1,3-bis((1H-pyrazol-3-yl)methyl)-2,3-dihydro-1H-imidazole, LH) was synthesized. Complex [LAu(III)Cl3] is an excellent catalyst for promoting dihydroalkoxylation at room temperature, even catalyzing this reaction at 0 °C. [LAu(III)Cl3] is one of the most efficient catalysts reported to date for the spirocyclization of alkynyl diols. Furthermore, [LAu(III)Cl3] catalyzed intra- and intermolecular hydroamination reactions, achieving good to excellent conversions. [LAu(III)Cl3] is a more efficient catalyst than a gold(I) analogue, [LAu(I)Cl]. The dependence of the quantity of weakly coordinating anion [BArF4]- ((3,5-trifluoromethyl)phenyl borate) present on catalysis efficiency was probed for the dihydroalkoxylation reaction. X-ray diffraction analysis of single crystals demonstrated the solid-state structure of gold complexes [LAu(III)Cl3] and [LAu(I)Cl], which displayed the expected square-planar and linear coordination geometries, respectively.
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Two new pincer ligands have been developed that contain a central N-heterocyclic carbene (NHC) moiety linked to two pendant pyrazole groups by either a methylene (NCN(me)) or ethylene (NCN(et)) chain. The coordination of these two ligands to rhodium and iridium resulted in a variety of binding modes. Tridentate coordination of the ligands was observed in the complexes [Rh(NCN(me))(COD)]BPh4 (8), [Ir(NCN(me))(COD)]BPh4 (10), [Rh(NCN(et))(CO)2]BPh4 (13), and [Ir(NCN(me))(CO)2]BPh4 (14), and monodentate NHC coordination was observed for [Ir(NCN(me))2(COD)]BPh4 (11) and [Ir(NCN(et))2(COD)]BPh4 (12). Both tridentate and bidentate coordination modes were characterized for [Rh(NCN(et))(COD)]BPh4 (9) in the solution and solid state, respectively, while an unusual bridging mode was observed for the bimetallic complex [Rh(µ-NCN(me))(CO)]2(BPh4)2 (15). The impact of this diverse coordination chemistry on the efficiency of the complexes as catalysts for the addition of NH, OH, and SiH bonds to alkynes was explored.
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The structural characterization of a (13)CO-labeled Ir(I) complex bearing an P,N-donor ligand (1-[2-(diphenylphosphino)ethyl]pyrazole), [Ir(PyP)((13)CO)Cl] is demonstrated using a series of tailored solid-state NMR techniques based on ultrafast (60 kHz) Magic Angle Spinning (MAS), which facilitates correlations with narrow proton line-widths. Our 1D (1)H MAS and 2D (13)C and (31)P CP-MAS NMR spectra provided structural information similar to that obtained using NMR spectroscopy in solution. We employed high-resolution 2D solid-state correlation spectroscopy ((1)H-(13)C HETCOR, (1)H-(31)P correlation) to characterize the networks of dipolar couplings between protons and carbon/phosphorus. (1)H-(1)H SQ-SQ correlation spectra showed the dipolar contacts between all protons in a similar fashion to its solution counterpart, NOESY. The use of the (1)H single quantum/double quantum experiments made it possible to observe the dipolar-coupling contacts between immediately adjacent protons. Additionally, internuclear (13)CO-(31)P distance measurements were performed using REDOR. The combination of all of these techniques made it possible to obtain comprehensive structural information on the molecule [Ir(PyP)((13)CO)Cl] in the solid state, which is in excellent agreement with the single crystal X-ray structure of the complex, and demonstrates the enormous value of ultrafast MAS NMR techniques for a broad range of future applications.
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A series of N,N-donor ligands (bis(pyrazol-1-yl)methane (bpm), bis(N-methylimidazol-2-yl)methane (bim), 1-(phenylmethyl)-4-(1H-pyrazol-1-yl methyl)-1H-1,2,3-triazole (PyT)), and one N,P-donor ligand precursor (1-(3,5-dimethylpyrazol-1-yl)(2-bromoethane) (dmPyBr)) were synthesized and functionalized with aniline. Diazotization of the aniline into an aryl diazonium, using nitrous acid in aqueous conditions, was performed in situ such that the ligands could be reductively adsorbed onto glassy carbon electrode surfaces. The N,N-donor ligands (bpm, bim, PyT) were immobilized in a single step, while several steps were required to immobilize the N,P-donor ligand (dmPyP) to prevent oxidation of the phosphine group. The complexation of the anchored ligands with the metal complex precursor ([Rh(CO)2(µ-Cl)]2) led to the formation of anchored Rh(I) complexes with each of the ligands (bpm, bim, PyT, dmPyP). X-ray photoelectron spectroscopy (XPS) confirmed the formation of the anchored ligands as well as the anchored complexes. The surface coverage of functionalized electrodes was estimated by means of cyclic voltammetry, and the nature of the coverage was close to being a monolayer for each immobilized complex. The anchored Rh(I) complexes were active as catalysts for the intramolecular hydroamination of 4-pentyn-1-amine to form 2-methyl-1-pyrroline.
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Paramagnetic effects from lanthanide ions present powerful tools for protein studies by nuclear magnetic resonance (NMR) spectroscopy provided that the lanthanide can be site-specifically and rigidly attached to the protein. A new, particularly small and rigid lanthanide-binding tag, 3-mercapto-2,6-pyridinedicarboxylic acid (3MDPA), was synthesized and attached to two different proteins via a disulfide bond. The complexes of the N-terminal domain of the E. coli arginine repressor (ArgN) with seven different paramagnetic lanthanide ions and Co(2+) were analyzed in detail by NMR spectroscopy. The magnetic susceptibility anisotropy (Delta chi) tensors and metal position were determined from pseudocontact shifts. The 3MDPA tag generated very different Delta chi tensor orientations compared to the previously studied 4-mercaptomethyl-DPA tag, making it a highly complementary and useful tool for protein NMR studies.
Assuntos
Proteínas de Escherichia coli/química , Elementos da Série dos Lantanídeos/química , Ácidos Picolínicos/química , Proteínas Repressoras/química , Compostos de Sulfidrila/química , Cobalto/química , Muramidase/química , Ressonância Magnética Nuclear Biomolecular , Ácidos Picolínicos/síntese química , Ligação Proteica , Estrutura Terciária de Proteína , Compostos de Sulfidrila/síntese químicaRESUMO
While dual photocatalysis-transition metal catalysis strategies are extensively reported, the majority of systems feature two separate catalysts, limiting the potential for synergistic interactions between the catalytic centres. In this work we synthesised a series of tethered dual catalysts allowing us to investigate this underexplored area of dual catalysis. In particular, Ir(i) or Ir(iii) complexes were tethered to a BODIPY photocatalyst through different tethering modes. Extensive characterisation, including transient absorption spectroscopy, cyclic voltammetry and X-ray absorption spectroscopy, suggest that there are synergistic interactions between the catalysts. The tethered dual catalysts were more effective at promoting photocatalytic oxidation and Ir-catalysed dihydroalkoxylation, relative to the un-tethered species, highlighting that increases in both photocatalysis and Ir catalysis can be achieved. The potential of these catalysts was further demonstrated through novel sequential reactivity, and through switchable reactivity that is controlled by external stimuli (heat or light).
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The enantiomers of the asymmetric, chiral platinum(II) complex [PtCl(2)(S-ahaz)] (S-ahaz = 3(S)-aminohexahydroazepine) each form two stereoisomers on binding to GpG sequences of DNA: one in which the primary amine is directed toward the 5' end of the DNA and one in which it is directed toward the 3' end. Previous binding studies have revealed that the S-enantiomer forms the two stereoisomers in a 7:1 ratio while the R-enantiomer forms them in close to a 1:1 ratio. In an attempt to elucidate the reasons behind the stereoselectivity displayed by the S-enantiomer and to establish which isomer is formed in the greater amount, we report here its reaction with a 14-mer oligodeoxyribonucleotide having a single GpG site. The two stereoisomers that formed were separated using HPLC methods, and their integrities were confirmed by electrospray ionization mass spectrometry. The DNA duplex was formed by combination of each of the purified reaction products with the complementary strand of DNA. Identification of both of the stereoisomers was achieved using 2D NMR spectroscopy, which is the first time this has been achieved for an unsymmetric platinum complex bound to DNA. The minor stereoisomer, with the bulk of the ahaz ring directed toward the 3' end of the platinated strand, induced considerable disruption to the 14-mer DNA duplex structure. The primary amine of the ahaz ligand was oriented toward the 3' side of the duplex in the major isomer, giving a DNA structure that was less disrupted and was more akin to the structure of the DNA on binding of cisplatin to the same sequence.
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DNA/química , Oligonucleotídeos/química , Compostos Organoplatínicos/química , Ligantes , Espectroscopia de Ressonância Magnética/métodos , Modelos Moleculares , Estereoisomerismo , Temperatura de TransiçãoRESUMO
The catalytic alkylation of ketones with alcohols via the hydrogen borrowing methodology (HB) has the potential to be a highly efficient approach for forming new carbon-carbon bonds. However, this transformation can result in more than one product being formed. The work reported here utilises bidentate triazole-carbene ligated iridium and rhodium complexes as catalysts for the selective formation of alkylated ketone or alcohol products. Switching from an iridium centre to a rhodium centre in the complex resulted in significant changes in product selectivity. Other factors - base, base loading, solvent and reaction temperature - were also investigated to tune the selectivity further. The optimised conditions were used to demonstrate the scope of the reaction across 17 ketones and 14 alcohols containing a variety of functional groups. A series of mechanistic investigations were performed to probe the reasons behind the product selectivity, including kinetic and deuterium studies.
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Two simple unsymmetrical monometallic Ir(i) complexes with an N-heterocyclic carbene ligand and an analogous bimetallic Ir(i) complex were synthesised. These complexes were found to be extremely active catalysts for a range of C-X (X = N or O) and Si-N bond forming reactions involving alkyne and imine activation for dihydroalkoxylation, hydroamination and hydrosilylation reactions. These catalysts exhibited reaction rates far exceeding those of other Rh(i) and Ir(i) complexes previously reported. In addition, a small change to the ligand design (phenyl vs. mesityl) substantially affected both the reactivity and product selectivity of the catalyst. The Ir(i) complex bearing a mesitylene wingtip provided unprecedented regioselectivity in the dihydroalkoxylation reaction and a new kinetic product from the typical hydrosilylation protocol of 2-benyzlpyrroline to produce an N-silylaminoalkene. Our mechanistic studies indicated that this transformation proceeded via a dehydrogenative coupling mechanism.
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A new lanthanide tag was designed for site-specific labeling of proteins with paramagnetic lanthanide ions. The tag, 4-mercaptomethyl-dipicolinic acid, binds lanthanide ions with nanomolar affinity, is readily attached to proteins via a disulfide bond, and avoids the problems of diastereomer formation associated with most of the conventional lanthanide tags. The high lanthanide affinity of the tag opens the possibility to measure residual dipolar couplings in a single sample containing a mixture of paramagnetic and diamagnetic lanthanides. Using the DNA-binding domain of the E. coli arginine repressor as an example, it is demonstrated that the tag allows immobilization of the lanthanide ion in close proximity of the protein by additional coordination of the lanthanide by a carboxyl group of the protein. The close proximity of the lanthanide ion promotes accurate determinations of magnetic susceptibility anisotropy tensors. In addition, the small size of the tag makes it highly suitable for studies of intermolecular interactions.
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Elementos da Série dos Lantanídeos/química , Ressonância Magnética Nuclear Biomolecular , Ácidos Picolínicos/química , Proteínas/química , Compostos de Sulfidrila/química , Proteínas de Bactérias/química , Proteínas de Escherichia coli/química , Estrutura Terciária de Proteína , Proteínas Repressoras/químicaRESUMO
The methylhydrazine complex [Ru(NH(2)NHMe)(PyP)(2)]Cl(BPh(4)) (PyP=1-[2-(diphenylphosphino)ethyl]pyrazole) was synthesised by addition of methylhydrazine to the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)(BPh(4))(2). The methylhydrazine ligand of the ruthenium complex has two different binding modes: side-on (eta(2)-) when the complex is in the solid state and end-on (eta(1)-) when the complex is in solution. The solid-state structure of [Ru(PyP)(2)(NH(2)NHMe)]Cl(BPh(4)) was determined by X-ray crystallography. 2D NMR spectroscopic experiments with (15)N at natural abundance confirmed that in solution the methylhydrazine is bound to the metal centre by only the -NH(2) group and the ruthenium complex retains an octahedral conformation. Hydrazine complexes [RuCl(PyP)(2)(eta(1)-NH(2)NRR')]OSO(2)CF(3) (in which R=H, R'=Ph, R=R'=Me and NRR'=NC(5)H(10)) were formed in situ by the addition of phenylhydrazine, 1,1-dimethylhydrazine and N-aminopiperidine, respectively, to a solution of the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)(OSO(2)CF(3))(2) in dichloromethane. These substituted hydrazine complexes of ruthenium were shown to exist in an equilibrium mixture with the bimetallic starting material.
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Hidrazinas/química , Compostos Organometálicos/química , Compostos Organometálicos/síntese química , Rutênio/química , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Estrutura Molecular , Soluções/químicaRESUMO
Parallel factor analysis (PARAFAC) was used to analyze data from the high throughput screening of an array of organometallic rhodium and iridium complexes as catalysts for the intramolecular hydroamination of 2-(2-phenylethynyl)aniline to give 2-phenylindole. The progress of the hydroamination reactions was monitored using UV-visible spectroscopy. The overlapped UV-visible spectra of the mixture of starting material, product and solvent in the samples taken at different times were deconvoluted using PARAFAC. Unique PARAFAC models led to close approximations of the actual UV-visible spectra of the compounds in the mixture. The performance of the catalysts was then compared by estimating the final concentration of the starting material and product using PARAFAC loadings. A library of 63 complexes generated in situ was examined in a single experiment using this methodology. The complexes were generated from combinations of seven ligands (bis(N-methyl2-imidazolyl)methane, bis(1-pyrazolyl)methane, 1,10-phenanthroline, N,N'-bis(p-tolyl)diazabutadiene, N,N'-bis(p-tolyl)1,2-dimethyldiazabutadiene, N,N'-bis(mesityl)1,2-dimethyldiazabutadiene and bis(2,4,6-trimethylphenylimino)acenapthene) and nine metal precursors ([Ir(COD)Cl](2) (COD = 1,5-cyclooctadiene), [Ir(CO)(2)Cl](n), [Ir(COE)(2)Cl](2), [IrCp*Cl(2)](2) (Cp* = 1,2,3,4,5-pentamethylcyclopentadiene), [Rh(COD)Cl](2), [Rh(CO)(2)Cl](2), [Rh(COE)(2)Cl](2), [RhCp*Cl(2)](2) and [RhCpCl(2)](2)) (Cp = cyclopentadiene)). The proposed method can be used for the fast screening of arrays of metal complexes for identifying effective catalysts, providing information that can augment traditional methods used for the analysis of catalyzed reactions.
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Irídio , Modelos Químicos , Ródio , Catálise , Eletroquímica , Indóis/química , Análise de Componente Principal , Espectrofotometria UltravioletaRESUMO
The catalytic signal amplification by reversible exchange process has become widely used for the hyperpolarisation of small molecules to improve their magnetic resonance detectability. It harnesses the latent polarisation of parahydrogen, and involves the formation of a labile metal complex that often contains an N-heterocyclic carbene (NHC) ligand (e.g. [Ir(H)2(NHC)(pyridine)3]Cl), which act as a polarisation transfer catalyst. Unfortunately, if the target molecule is too bulky, binding to the catalyst is poor and the hyperpolarisation yield is therefore low. We illustrate here the behaviour of a series of asymmetric NHC containing catalysts towards 3,4- and 3,5-lutidine in order to show how catalyst design can be used to dramatically improve the outcome of this catalytic process for sterically encumbered ligands.
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Multivalent circular aptamers or 'captamers' have recently been introduced through the merger of aptameric recognition functions with the basic principles of DNA nanotechnology. Aptamers have strong utility as protein-binding motifs for diagnostic applications, where their ease of discovery, thermal stability and low cost make them ideal components for incorporation into targeted protein assays. Here we report upon a property specific to circular DNA aptamers: their intrinsic compatibility with a highly sensitive protein detection method termed the 'proximity extension' assay. The circular DNA architecture facilitates the integration of multiple functional elements into a single molecule: aptameric target recognition, nucleic acid hybridization specificity and rolling circle amplification. Successful exploitation of these properties is demonstrated for the molecular analysis of thrombin, with the assay delivering a detection limit nearly three orders of magnitude below the dissociation constants of the two contributing aptamer-thrombin interactions. Real-time signal amplification and detection under isothermal conditions points towards potential clinical applications, with both fluorescent and bioelectronic methods of detection achieved. This application elaborates the pleiotropic properties of circular DNA aptamers beyond the stability, potency and multitargeting characteristics described earlier.
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DNA Circular/química , Técnicas de Amplificação de Ácido Nucleico , Oligodesoxirribonucleotídeos/química , Proteínas/análise , Aptâmeros de Nucleotídeos , Sítios de Ligação , Primers do DNA , DNA Circular/biossíntese , DNA Circular/metabolismo , Humanos , Oligodesoxirribonucleotídeos/biossíntese , Oligodesoxirribonucleotídeos/metabolismo , Oligonucleotídeos/química , Trombina/análise , Fatores de TempoRESUMO
Two highly versatile xanthene scaffolds containing pairs of heteroditopic ligands were found to be capable of accommodating a range of transition metal ions, including Au(i), Ir(i), Ir(iii), Rh(i), and Ru(ii) to generate an array of heterobimetallic complexes. The metal complexes were fully characterised and proved to be stable in the solid and solution state, with no observed metal-metal scrambling. Heterobimetallic complexes containing the Rh(i)/Ir(i) combinations were tested as catalysts for the two-step dihydroalkoxylation reaction of alkynediols and sequential hydroamination/hydrosilylation reaction of alkynamines.
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Rh(i) and Ir(i) homobimetallic complexes were synthesised using a heteroditopic ligand system on a xanthene scaffold containing a monodentate N-heterocyclic carbene ligand and a bidentate bis(pyrazol-1-yl)methane ligand. The complexes were tested as catalysts for the two-step dihydroalkoxylation and two-step hydroamination/hydrosilylation reactions. This is the first known report of an organometallic group 9 complex, Ir(i) bimetallic complex, 13, to selectively favour the opposite spirocyclisation product from that reported in the literature, 14cvs.14b. The Ir(i) homobimetallic complex catalyses the intramolecular hydroamination reaction of alkynamines efficiently and proved to be a highly active catalyst for promoting the subsequent hydrosilylation of the pyrrolines; completing the hydrosilylation reactions in less than 40 seconds. A chloro-bridged bimetallic species was observed in the solid state, revealing that the COD co-ligands present underwent an oxidation.
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Correction for 'Enhancements in catalytic reactivity and selectivity of homobimetallic complexes containing heteroditopic ligands' by Mark R. D. Gatus et al., Dalton Trans., 2017, 46, 7457-7466.
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Strategies for combining the selectivity and efficiency of homogeneous organometallic catalysts with the versatility of heterogeneous catalysts are urgently needed. Herein a direct and modular methodology is presented that provides rapid access to well-defined carbon-rhodium hybrid catalysts. A pre-synthesized Rh(i) complex containing a carbene-triazole ligand was found to be stable for direct immobilization onto unactivated graphene, carbon black and glassy carbon electrodes. Characterization of the heterogeneous systems using X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), inductively coupled plasma-optical emission spectroscopy/mass spectrometry (ICP-OES/MS), Raman spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) confirmed the well-defined nature of the hybrid catalysts. The hybrid catalysts show excellent activity, comparable to that of the homogeneous system for the hydrosilylation of diphenylacetylene, with turnover numbers ranging from 5000 to 48 000. These catalysts are the best reported to date for the hydrosilylation of diphenylacetylene. In common with conventional heterogeneous catalysts, high reusability, due to a lack of Rh metal leaching, was also observed for all carbon-rhodium complexes under investigation.
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A series of Ru(ii) complexes were synthesised based on a hemilabile pyrazole-N-heterocyclic carbene (NHC)-pyrazole (C3N2H3)CH2(C3N2H2)CH2(C3N2H3) NCN pincer ligand 1. All complexes were fully characterised using single crystal X-ray crystallography and multinuclear NMR spectroscopy. Hemilabile ligands provide flexible coordination modes for the coordinating metal ion which can play a significant effect on the efficiency and mechanism of catalysis by the resulting complex. Here we observed and isolated mono-, bi- and tri-dentate complexes of both Ag(i) and Ru(ii) with 1 in which the resultant coordination mode was controlled by careful reagent selection. The catalytic activity of the Ru(ii) complexes for the transfer hydrogenation reaction of acetophenone with isopropanol was investigated. The unexpected formation of the pentaborate anion, [B5O6(OH)4](-), during the synthesis of complex 6a was found to have an unexpected positive effect by enhancing the catalysis rate. This work provides insights into the roles that different coordination modes, counterions and ligand hemilability play on the catalytic activity in transfer hydrogenations.