A Bis(µ‐chlorido)‐Bridged Cobalt(II) Complex with Silyl‐Containing Schiff Base as a Catalyst Precursor in the Solvent‐Free Oxidation of Cyclohexane

Zaltariov, Mirela‐Fernanda; Vieru, Veacheslav; Zalibera, Michal; Cazacu, Maria; Martins, Nuno M. R.; Martins, Luísa M. D. R. S.; Rapta, Peter; Novitchi, Ghénadie; Shova, Sergiu; Pombeiro, Armando J. L.; Arion, Vladimir B.

doi:10.1002/ejic.201700875

Cited by 15 publications

(3 citation statements)

References 62 publications

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“…However, many examples show that the optimal functional is not transferable from system to system. For example, it was observed that B3LYP [47,48] can give satisfactory results for copper [54][55][56][57] and cobalt [58,59] complexes, but is not the best functional for chromium [60], manganese [61] and iron [62] dimers. In these latter cases, TPSS0 [63,64], TPSSh [65] and M06 [66], respectively, are the best performing functionals to describe the experimental results.…”

Section: B Broken-symmetry Density Functional Theorymentioning

confidence: 99%

Magnetic exchange coupling in Cu dimers studied with modern multireference methods and broken-symmetry coupled cluster theory

et al. 2021

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Spin-state energetics of exchange-coupled copper complexes pose a persistent challenge for applied quantum chemistry. Here, we provide a comprehensive comparison of all available theoretical approaches to the problem of exchange coupling in two antiferromagnetically coupled bis-μ-hydroxo Cu(II) dimers. The evaluated methods include multireference methods based on the density matrix renormalization group (DMRG), multireference methods that incorporate dynamic electron correlation either perturbatively, such as the N-electron valence state perturbation theory, or variationally, such as the difference-dedicated configuration interaction. In addition, we contrast the multireference results with those obtained using broken-symmetry approaches that utilize either density functional theory or, as demonstrated here for the first time in such systems, a local implementation of coupled cluster theory. The results show that the spin-state energetics of these copper dimers are dominated by dynamic electron correlation and represent an impossible challenge for multireference methods that rely on brute-force expansion of the active space to recover correlation energy. Therefore, DMRG-based methods even at the limit of their applicability cannot describe quantitatively the antiferromagnetic exchange coupling in these dimers, in contrast to dinuclear complexes of earlier transition metal ions. The convergence of the broken-symmetry coupled cluster approach is studied and shown to be a limiting factor for the practical application of the method. The advantages and disadvantages of all approaches are discussed, and recommendations are made for future developments.

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Section: B Broken-symmetry Density Functional Theorymentioning

confidence: 99%

Magnetic exchange coupling in Cu dimers studied with modern multireference methods and broken-symmetry coupled cluster theory

et al. 2021

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“…Therefore, developing new highly efficient and robust heterogeneous catalysts for industrial-scale selective aerobic oxidation of cyclohexane is of great importance. In the last several years, various heterogeneous catalysts have been widely exploited for cyclohexane catalytic aerobic oxidation. − For example, supported metalloporphyrins, − transition metals with Schiff base ligands, , cobalt compounds, − copper complexes, − and metal nanoparticles − have been developed to promote the cyclohexane conversion and the selectivity of KA oil under relatively mild and environmentally friendly reaction conditions. However, most of these catalyst systems either required high temperature/pressure or suffered from poor selectivity to KA oil.…”

Section: Introductionmentioning

confidence: 99%

Ionic Liquid-Modified Co/ZSM-5 Catalyzed the Aerobic Oxidation of Cyclohexane: Toward Improving the Activity and Selectivity

Hong

Fang

Zhou

et al. 2019

Ind. Eng. Chem. Res.

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Ionic liquid (IL)-modified metal/ZSM-5 composites served as heterogeneous catalysts toward cyclohexane aerobic oxidation, demonstrating excellent KA oil (cyclohexanol and cyclohexanone) selectivity with improved activity. The effects of the different functional groups of the IL on the oxidation were further systematically investigated. The catalytic activity of the catalyst was closely related to the anionic group of the IL, whereas the cationic group had no obvious effects. The cyclohexane conversion and selectivity of KA oil reached 9.7 and 92.2%, respectively, using the optimized catalyst C6mimHSO4-Co/ZSM-5. This favorable catalytic performance was mainly attributed to the activation of the cyclohexane by the anionic group of the IL, whereas the excellent selectivity was ascribed to the superior solubility of KA oil in the IL while avoiding overoxidation. Based on the results of in situ electron paramagnetic resonance spectra, a catalytic mechanism involving a free-radical process was also proposed.

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“…Koordinasyon bileşikleri, bilim ve teknolojideki geniş uygulama alanları nedeniyle özel ilgi konusu olmuştur [1][2][3]. Özellikle Schiff baz ligandı içeren geçiş metali kompleksleri, çoğunlukla kataliz [4,5], kemosensörler [6,7], lüminesans malzemeler [8,9], enerji malzemeleri [10,11], manyetik-yapısal kimya [12,13] ve biyolojik alanlar [14][15][16][17] gibi çeşitli alanlardaki önemli uygulamaları nedeniyle dikkat çekmektedir. Schiff baz kompleksleri, kullanılan aldehit ve amine bağlı olarak, ligandlar için çok çeşitli olası yapılar oluşturabilmesi nedeniyle, yıllar içinde önemli ölçüde ilgi odağı olan konular arasında yer almıştır [18].…”

Section: Introductionunclassified

Hidrazon Türevi Yeni Fe(II), Co(II), Ni(II) ve Cu(II) Komplekslerinin Sentezi ve Karakterizasyonu

Soğukömeroğulları

Başaran

2022

Süleyman Demirel Üniversitesi Fen Bilimleri Enstitüsü Dergisi

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N-((2-hydroxynaphthalen-1-yl)methylene)nicotinohydrazide ligand derived from the condensation reaction of 2-hydroxynaphthaldehyde and nicotinic hydrazide was obtained. New hydrazone metal complexes L2Fe, L2Co, L2Ni and L2Cu2 were synthesized from the reaction of N-((2-hydroxynaphthalen-1-yl)methylene)nicotinohydrazide ligand and Fe(II), Co(II), Ni(II) and Cu(II) acetate salts in a 2:1 stoichiometric ratio, respectively. The synthesized compounds were characterized by techniques such as FT-IR, NMR (ligand only), UV-Vis, elemental analysis, molar conductivity measurement, magnetic susceptibility. Magnetic susceptibility measurements were recorded as 5.96 BM, 1.03 BM, 1.08 BM and 1.61 BM for the L2Fe, L2Co L2Ni and L2Cu2 complexes, respectively. It has been determined that the L2Cu2, L2Ni and L2Co complexes have antiferromagnetic properties. The L2Fe, L2Co and L2Ni complexes have octahedral geometry, while the L2Cu2 complex has a square plane geometry. The molar conductivity values of the complexes are between 1.31-2.61 μS/cm and do not have conductivity properties.

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A Bis(µ‐chlorido)‐Bridged Cobalt(II) Complex with Silyl‐Containing Schiff Base as a Catalyst Precursor in the Solvent‐Free Oxidation of Cyclohexane

Cited by 15 publications

References 62 publications

Magnetic exchange coupling in Cu dimers studied with modern multireference methods and broken-symmetry coupled cluster theory

Magnetic exchange coupling in Cu dimers studied with modern multireference methods and broken-symmetry coupled cluster theory

Ionic Liquid-Modified Co/ZSM-5 Catalyzed the Aerobic Oxidation of Cyclohexane: Toward Improving the Activity and Selectivity

Hidrazon Türevi Yeni Fe(II), Co(II), Ni(II) ve Cu(II) Komplekslerinin Sentezi ve Karakterizasyonu

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