Air-stable Cobalt Research Articles

Unveiling the Reactivity of Part Per Million Levels of Cobalt-Salen Complexes in Hydrosilylation of Ketones.

A series of air-stable cobalt(III)salen complexes Co-1 to Co-4 have been synthesized and employed in the hydrosilylation of ketones. Notably, the most intricately tailored Co-3 pre-catalyst exhibited exceptional catalytic activity under mild reaction conditions. The developed catalytic hydrosilylation protocol proceeded with an unusual ppm level (5 ppm) catalyst loading of Co-3 and achieved a maximum turnover number (TON) of 200,000. A wide variety of aromatic, aliphatic, and heterocyclic ketones encompassing both electron-donating and electron-withdrawing substituents were successfully transformed into the desired silyl ethers or secondary alcohols in moderate to excellent yields.

Air-Stable Cobalt(III) and Chromium(III) Complexes as Single-Component Catalysts for the Activation of Carbon Dioxide and Epoxides.

Cobalt(III) and chromium(III) salophen chloride complexes were synthesized and tested for the cycloaddition of carbon dioxide (CO2) with epoxides to obtain cyclic carbonates. The cat1, cat2, cat4, and cat5 complexes presented high catalytic activity without cocatalysts and are solvent-free at 100 °C, 8 bar, and 9 h. At these conditions, the terminal epoxides (1a-1k) were successfully converted into the corresponding cyclic carbonates with a maximum conversion of ∼99%. Moreover, cat5 was highlighted due to its capability of opening internal epoxides such as limonene oxide (1l) with a 36% conversion to limonene carbonate (2l), and from cyclohexene oxide (1m), cyclic trans-cyclohexene carbonate (2m) and poly(cyclohexene carbonate) were obtained with 15% and 85% selectivity, respectively. A study of the coupling reaction mechanism was proposed with the aid of electrospray ionization mass spectrometry (ESI-MS) analysis, confirming the single-component behavior of the complexes through their ionization due to epoxide coordination. In addition, crystallographic analysis of cat1 single crystals grown in a saturated solution of pyridine helped to demonstrate that the substitution of chloride ion by pyridine ligands to form an octahedral coordination occurs (Py-cat1), supporting the proposed mechanism. Also, a recyclability study was performed for cat5, and a total turnover number of 952 was obtained with only minor losses in catalytic activity after five cycles.

Synthesis of imines from the coupling reaction of alcohols and amines catalyzed by phosphine-free cobalt(II) complexes.

Phosphine-free, air stable cobalt(II) based complexes (1a and 1b) consisting of ligands L1H2 and L2H2 (L1H2 = N,N'-((1,2-phenylenebis(azaneylylidene))bis(methaneylylidene))diphenol and L2H2 = N,N'-bis(4-diethylaminosalicylidene)-4,5-dichloro-1,2-phenylenediamine) were synthesized and utilized as catalysts in the coupling reaction of alcohols with amines into imines following an acceptorless dehydrogenative pathway. The reactions were carried out in the presence of t-BuOK base with low catalyst loading (1 mol%) in an open atmosphere. The corresponding imines were isolated in moderate to excellent yields. The methodology was screened with different substituted alcohols and amines. The proposed mechanistic pathway of this reaction was ascertained through intermediate mass and 1H NMR analyses. Most of the previously reported 3d transition metal catalysts used in imine synthesis reactions have a phosphine ligand environment, and the reactions were performed under inert conditions. Herein we have developed a sustainable route for the synthesis of imines from the coupling reaction of alcohols with amines under aerial reaction conditions using phosphine-free air stable cobalt catalysts.

Phenoxythiazoline (FTz)-Cobalt(II) Precatalysts Enable C(sp2 )-C(sp3 ) Bond-Formation for Key Intermediates in the Synthesis of Toll-like Receptor 7/8 Antagonists.

Evaluation of the relative rates of the cobalt-catalyzed C(sp2 )-C(sp3 ) Suzuki-Miyaura cross-coupling between the neopentylglycol ester of 4-fluorophenylboronic acid and N-Boc-4-bromopiperidine established that smaller N-alkyl substituents on the phenoxyimine (FI) supporting ligand accelerated the overall rate of the reaction. This trend inspired the design of optimal cobalt catalysts with phenoxyoxazoline (FOx) and phenoxythiazoline (FTz) ligands. An air-stable cobalt(II) precatalyst, (FTz)CoBr(py)3 was synthesized and applied to the cross-coupling of an indole-5-boronic ester nucleophile with a piperidine-4-bromide electrophile that is relevant to the synthesis of reported toll-like receptor (TLR) 7/8 antagonist molecules including afimetoran. Addition of excess KOMe⋅B(Oi Pr)3 improved catalyst lifetime due to attenuation of alkoxide basicity that otherwise resulted in demetallation of the FI chelate. A first-order dependence on the cobalt precatalyst and a saturation regime in nucleophile were observed, supporting turnover-limiting transmetalation and the origin of the observed trends in N-imine substitution.

Surfactant-free synthesis and magnetic property evaluation of air-stable cobalt oxide nanostructures

We report the synthesis of metastable cobalt oxide (CoO) nanostructures via the low-temperature microwave-assisted solvothermal (MAS) process. An alcoholic solution of cobalt (II) acetylacetonate in a sealed vessel was irradiated with microwaves at a temperature <150 °C and a pressure below 100 psi. As-synthesized powder material was characterized in terms of its structure and morphology. X-ray diffractometry (XRD) indicates the formation of well-crystallized CoO nanoparticles without the need for post-synthesis annealing. The mean crystallite size of the nanoparticles was estimated to be 41 nm. The morphology of the as-prepared powder sample was evaluated by field-emission scanning electron microscopy (FESEM), which revealed the formation of densely packed nanospheres of diameter <100 nm. The CoO nanospheres were obtained without the need for any surfactants or capping agents; they were found to be quite resistant to oxidation in ambient air over several months. We attribute the stability of CoO nanospheres to their dense packing, the driving force being the minimization of surface energy and surface area. Fourier-transform infrared (FT-IR) spectroscopy and Raman spectroscopy confirm the formation of phase-pure CoO nanostructures. The deconvolution of the active modes in Raman spectra obtained at room temperature reveals the Oh symmetry in rock-salt CoO produced by the MAS route. We have analyzed its effect on the magnetic characteristics of the CoO nanostructures. Isothermal field-dependent magnetization (MH) and inverse magnetic susceptibility measurements show a phase transition from antiferromagnetic to ferromagnetic interactions in the CoO nanostructures at around 10 K. The results indicate that the phenomenon of magnetic phase transition as a function of temperature is unique to CoO nanoparticles. This finding reveals the magnetic behavior of CoO nanostructures and presents opportunities for its possible application as an anisotropy source for magnetic recording.

Hydrogenation and dehydrogenation of N-heterocycles under Cp*Co(III)-catalysis.

To realize the goal of a carbon-free energy economy, it is crucial to discover reactions that utilize sustainable resources as alternatives to fossil feedstocks. In this study, a well-defined, air-stable Cp*Co(III)-catalyst for transfer hydrogenation of quinoline derivatives and oxidative dehydrogenation of cyclic amines in water is developed. While the former reaction is promoted by formic acid as a transfer hydrogenation reagent, the latter is mediated by molecular oxygen as the sole oxidant. These processes provide new avenues for the investigation of air-stable cobalt catalysts for environmentally benign hydrogenation and dehydrogenation reactions.

New Co and Mn Catalysts Bearing ONO Ligands Containing Nucleophile for the Coupling of CO2 and Propylene Oxide

A series of novel ONO ligands bearing an ionic pendant-armed (hereinafter indicated as ONONu, where Nu corresponds to an anionic nucleophile) were synthesized, characterized, and successfully coordinated to cobalt and manganese precursors. New air-stable cobalt (III) complexes (1–6) and manganese (II) complexes (7 and 8) were obtained and characterized. Single crystal X-ray diffraction analysis of the Co(III) compound 5 confirmed the presence of two quaternized ligands coordinated to the metal and iodide as counterion. These novel complexes were revealed to be active catalysts in the coupling reaction of carbon dioxide and propylene oxide (PO) in different degrees of success. Among these, the manganese complex 8 afforded the best results towards the formation of propylene carbonate (PC) with a productivity of 256 kg PC/(kg cat·h), achieving a TON of 4860.

Alcohol Synthesis by Cobalt-Catalyzed Visible-Light-Driven Reductive Hydroformylation

A cobalt-catalyzed reductive hydroformylation of terminal and 1,1-disubstituted alkenes is described. One-carbon homologated alcohols were synthesized directly from CO and H2, affording anti-Markovnikov products (34-87% yield) with exclusive regiocontrol (linear/branch >99:1) for minimally functionalized alkenes. Irradiation of the air-stable cobalt hydride, (dcype)Co(CO)2H (dcype = dicyclohexylphosphinoethane) with blue light generated the active catalyst that mediates alkene hydroformylation and subsequent aldehyde hydrogenation. Mechanistic origins of absolute regiocontrol were investigated by in situ monitoring of the tandem catalytic reaction using multinuclear NMR spectroscopy with syngas mixtures.

Old Dog, New Tricks: Innocent, Five-coordinate Cyanocobalt Corroles.

Three mono-CN ligated anionic cobalt A3-triarylcorroles were synthesized and investigated as to their spectroscopic and electrochemical properties in CH2Cl2, pyridine (Py), and dimethyl sulfoxide (DMSO). The newly synthesized corroles provide the first examples of air-stable cobalt corroles with an anionic axial ligand and are represented as [(Ar)3CorCoIII(CN)]-TBA+, where Cor is the trivalent corrole macrocycle, Ar is p-(CN)Ph, p-(CF3)Ph, or p-(OMe)Ph, and TBA+ is the tetra-n-butylammonium (TBA) cation. Multiple redox reactions are observed for each mono-CN derivative with a key feature being a more facile first oxidation and a more difficult first reduction in all three solvents as compared to all previously examined corroles with similar meso- and β-pyrrole substituents. Formation constants (log K) for conversion of the five-coordinate mono-CN complex to its six-coordinate bis-CN form ranged from 102.8 for Ar = p-(OMe)Ph to 104.7 for Ar = p-(CN)Ph in DMSO as determined by spectroscopic methodologies. The in situ generated bis-CN complexes, represented as [(Ar)3CorCoIII(CN)2]2-(TBA+)2, and the mixed ligand complexes, represented as [(Ar)3CorCoIII(CN)(Py)]-TBA+, were also investigated as to their electrochemical and spectroscopic properties. UV-visible spectra and electrode reactions of the synthesized mono-CN derivatives are compared with the neutral mono-DMSO cobalt corrole complexes and the in situ generated bis-CN and bis-Py complexes, and the noninnocent (or innocent) nature of each cobalt corrole system is addressed. The data demonstrate the ability of the CN- axial ligand(s) to stabilize the high-valent forms of the metallocorrole, leading to systems with innocent macrocyclic ligands. Although a number of six-coordinate cobalt(III) corroles with N-donor ligands were characterized in the solid state, a dissociation of one axial ligand readily occurs in nonaqueous solvents, and this behavior contrasts with the high stability of the currently studied bis-CN adducts in CH2Cl2, pyridine, or DMSO. Linear free energy relationships were elucidated between the meso-phenyl Hammett substituent constants (Σσ) and the measured binding constants, the redox potentials, and the energy of the band positions in the mono-CN and bis-CN complexes in their neutral or singly oxidized forms, revealing highly predictable trends in the physicochemical properties of the anionic corroles.

Homogeneous Electrochemical Reduction of CO2 to CO by a Cobalt Pyridine Thiolate Complex.

The chemical and electrochemical reduction of CO2 to value added chemicals entails the development of efficient and selective catalysts. Synthesis, characterization and electrochemical CO2 reduction activity of a air-stable cobalt(III) diphenylphosphenethano-bis(2-pyridinethiolate)chloride [{Co(dppe)(2-PyS)2}Cl, 1-Cl] complex is divulged. The complex reduces CO2 under homogeneous electrocatalytic conditions to produce CO with high Faradaic efficiency (FE > 92%) and selectivity in the presence of water. Through detailed electrochemical investigations, product analysis, and mechanistic investigations supported by theoretical calculations, it is established that complex 1-Cl reduces CO2 in its Co(I) state. A reductive cleavage leads to a dangling protonated pyridine arm which enables facile CO2 binding through a H-bond donation and facilitates the C-O bond cleavage via a directed protonation. A systematic benchmarking of this catalyst indicates that it has a modest overpotential (∼180 mV) and a TOF of ∼20 s-1 for selective reduction of CO2 to CO with H2O as a proton source.

Ultrasensitive detection of rutin antioxidant through a magnetic micro-mesoporous graphitized carbon wrapped Co nanoarchitecture

Ultrasensitive sensing of organic compounds has attracted a great deal of attention in recent years. Here, we report air-stable cobalt decorated-nanoporous carbon (Co/ZIF-C), derived from the pyrolysis of zeolitic imidazolate based metal-organic framework (ZIF-67), for ultrasensitive detection of flavonoid, rutin. In line with this, we examined the electrosensing activity of Co/ZIF-C in the presence of rutin and found that it could be a promising agent for sensing of formaldehyde, toluene and hydrogen gases. In the structure of Co/ZIF-C, Co synergizes the sensing performance and hence, shows a superior activity compared to the commercially available forms of carbon nanostructures (e.g. carbon nanotube (CNT) and graphene). The designed sensor, Co/ZIF-C/GCE (GCE, glassy carbon electrode), exhibits sensitivity ca 2.5, 1.5, 22.6 and 125.0 times more than the Co-etched Co/ZIF-C, SWCNT/GCE, rGO/GCE and bare GCE, respectively. The linear range, quantification (LOQ) and detection (LOD) limits of rutin sensor with Co/ZIF-C/GCE were found to be 0.1–30 μM, 73 and 22 nM, respectively. The Co/ZIF-C/GCE sensor is demonstrated to be highly selective toward rutin in the presence of other interfering ions, biomolecules and antioxidants. In addition, the newly developed electrochemical technique was approved by HPLC to determine rutin antioxidant in mixed vitamin tablet samples.

Cobalt(iii)-catalyzed ketone-directed C–H vinylation using vinyl acetate

Weakly coordinating, ketone-directed C–H vinylation using vinyl acetate is reported here for a wide range of aromatic ketones such as acetophenones, diaryl ketones, chromones and chalcones under cost-effective and air-stable cobalt(iii)-catalysis.

Cobalt-catalyzed regioselective hydrohydrazination of epoxides.

Using an air-stable cobalt catalyst [Cp*Co(1,2-Ph2PC6H4S)(NCMe)]BF4 (1, Cp* = Me5C5-), we have achieved catalytic regioselective hydrohydrazination of epoxides to 1,1-hydrazinoalcohols in an atom-economical manner. The catalysis involves a cobalt-hydrazine intermediate, in which the NH2 group of the hydrazine binds to the metal center, inhibiting its nucleophilic reactivity and allowing the NH group to participate in the regioselective hydrohydrazination.

Cobalt-Catalyzed Alkoxycarbonylation of Epoxides to β-Hydroxyesters.

Herein, we developed a new and practical catalytic system for the carbonylative synthesis of β-hydroxyesters. By using simple, cheap, and air-stable cobalt(II) bromide as the catalyst, combined with pyrazole and catalytic amount of manganese, active cobalt complex can be generated in situ and can catalyze various epoxides to give the corresponding β-hydroxyesters in moderate to excellent yields. Mechanism studies indicate that pyrazole plays a crucial role in this reaction. Moreover, with the addition of the catalytic amount of manganese, the active cobalt catalyst can be regenerated, which provides a possibility for reusing the cobalt catalyst.

Cp*Co(iii)-catalyzed annulation of azines by C-H/N-N bond activation for the synthesis of isoquinolines.

Herein, an efficient, atom economic and external oxidant free approach has been disclosed for the synthesis of isoquinolines. Azines were employed for annulation reactions with alkynes via sequential C-H/N-N bond activation using an air-stable cobalt catalyst. The method takes advantage of the incorporation of both the nitrogen atoms of azines into the desired isoquinoline products, offering the highest atom economy. In addition, the developed protocol works under external oxidant as well as silver salt free conditions. Furthermore, the established methodology features a relatively broad substrate scope with high product yields and scalability up to the gram level.

Markovnikov-Selective Hydroboration of Vinylarenes Catalyzed by a Cobalt(II) Coordination Polymer.

Highly efficient and practical hydroboration of alkenes has been catalyzed by an inexpensive and air-stable cobalt(II) coordination polymer (CP) in the presence of KO tBu. Complete conversion of alkenes to alkylboronates were performed within just 5 min with low catalyst loading (0.025 mol %), achieving the record high turnover frequencies of up to 47 520 h-1. For a range of vinylarenes, unusual Markovnikov selectivity was observed.

Competitive interplay of deposition and etching processes in atomic layer growth of cobalt and nickel metal films

Abstract

Cobalt-promoted regioselective preparation of aryl tetrazole amines

A highly general, efficient and simple methodology for the regioselective synthesis of aryl tetrazole amines has been explored. The present method involves consecutive desulphurization and $$C\hbox {-}N$$ cross-coupling reaction. Cheap, readily available and air stable cobalt catalyst has been used for this methodology. In addition, the substrate scope has been demonstrated. A highly general, efficient and simple methodology for the regioselective synthesis of aryl tetrazole amines has been explored. The present method involves consecutive desulphurization and $$C\hbox {-}N$$ cross-coupling reaction.

Insights into Activation of Cobalt Pre-Catalysts for C(sp2)-H Functionalization.

The activation of readily prepared, air-stable cobalt (II) bis(carboxylate) pre-catalysts for the functionalization of C(sp2)-H bonds has been systematically studied. With the pyridine bis(phosphine) chelate, iPrPNP, treatment of 1-(O2CtBu)2 with either B2Pin2 or HBPin generated cobalt boryl products. With the former, reduction to (iPrPNP)CoIBPin was observed while with the latter, oxidation to the cobalt(III) dihydride boryl, trans-(iPrPNP)Co(H)2BPin occurred. The catalytically inactive cobalt complex, Co[PinB(O2CtBu)2]2, accompanied formation of the cobalt-boryl products in both cases. These results demonstrate that the pre-catalyst activation from cobalt(II) bis(carboxylates), although effective and utilizes an air-stable precursor, is less efficient than activation of cobalt(I) alkyl or cobalt(III) dihydride boryl complexes, which are quantitatively converted to the catalytically relevant cobalt(I) boryl. Related cobalt(III) dihydride silyl and cobalt(I) silyl complexes were also synthesized from treatment of trans-(iPrPNP)Co(H)2BPin and (iPrPNP)CoPh with HSi(OEt)3, respectively. No catalytic silylation of arenes was observed with either complex likely due to the kinetic preference for reversible C-H reductive elimination rather than product- forming C-Si bond formation from cobalt(III). Syntheses of the cobalt(II) bis(carboxylate) and cobalt(I) alkyl of iPrPONOP, a pincer where the methylene spacers have been replaced by oxygen atoms, were unsuccessful due to deleterious P-O bond cleavage of the pincer. Despite their structural similarity, the rich catalytic chemistry of iPrPNP was not translated to iPrPONOP due to the inability to access stable cobalt precursors as a result of ligand decomposition via P-O bond cleavage.

C(sp2)-H Borylation of Fluorinated Arenes Using an Air-Stable Cobalt Precatalyst: Electronically Enhanced Site Selectivity Enables Synthetic Opportunities.

Cobalt catalysts with electronically enhanced site selectivity have been developed, as evidenced by the high ortho-to-fluorine selectivity observed in the C(sp2)-H borylation of fluorinated arenes. Both the air-sensitive cobalt(III) dihydride boryl 4-Me-(iPrPNP)Co(H)2BPin (1) and the air-stable cobalt(II) bis(pivalate) 4-Me-(iPrPNP)Co(O2CtBu)2 (2) compounds were effective and exhibited broad functional group tolerance across a wide range of fluoroarenes containing electronically diverse functional groups, regardless of the substitution pattern on the arene. The electronically enhanced ortho-to-fluorine selectivity observed with the cobalt catalysts was maintained in the presence of a benzylic dimethylamine and hydrosilanes, overriding the established directing-group effects observed with precious-metal catalysts. The synthetically useful selectivity observed with cobalt was applied to an efficient synthesis of the anti-inflammatory drug flurbiprofen.