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Budnikova, Yu. G.; Kafiyatullina, A. G.; Kargin, Yu. M.; Sinyashin, Оleg G.

doi:10.1023/a:1025676605941

Cited by 11 publications

(7 citation statements)

References 6 publications

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“…For Co(PPh 3 ) 2 Cl 2 , Co(dppb)Cl 2 , and Co(dppf)Cl 2 , only cathodic peaks with E p,c = −1.3, −1.5, and −1.35 V, respectively, were observed on the CV patterns on the GC electrode, while corresponding anodic counterpeaks were not detected (Figure ), indicating electrochemically irreversible processes, which can be assigned to Co 2+ /Co + . The results of the study of Co(PPh 3 ) 2 Cl 2 are consistent with the previously published results of studies of Co complexes with triphenylphosphine, obtained in situ from Co(BF 4 ) 2 and PPh 3 , where only irreversible or quasi-reversible processes were observed at different Co/L ratios at Au or GC electrodes . These processes could be assigned to Co I compound formation.…”

Section: Resultssupporting

confidence: 90%

Redox Behavior of Cobalt–Phosphine Complexes vs Their Catalytic Activity in Organozinc Compound Formation: Background for Mechanistic Investigations

et al. 2023

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Catalytic activity in arylzinc compound formation was studied for eight Co complexes with phosphines along with their redox properties for implementing the idea of rational design. It was found that Co(XantPhos)Cl 2 and Co(N-XantPhos)Cl 2 demonstrated distinct reversible Co II /Co I redox processes and acted as efficient catalysts of arylzinc compound formation. Meanwhile, for Co(DPEphos)Cl 2 , Co(dppf)Cl 2 , Co(dppb)Cl 2 , Co(PPh 3 ) 2 Cl 2 , and Co(XantPhos)(Piv) 2 (the latter one without the addition of LiCl), reversible redox processes were not observed. These catalysts did not act efficiently for the model process of organozinc compound formation. Co 4 (dppe) 5 Cl 8 was the only exception, explained by a completely different structure (CoP 4 Cl and CoPCl 3 ) of donor sets instead of CoP 2 X 2 (X = Cl or O). The stability of complexes in tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) solutions was studied by UV−vis spectroscopy. Previously unknown X-ray structures for Co(XantPhos)(Piv) 2 , Co(N-XantPhos)Cl 2 , and {Co(DMF) 6 }-{(CoCl 3 ) 2 (dppb)} were determined. The use of pivalate counterions instead of chloride for Co(XantPhos) 2+ led to a significant (ca. 20 times) increase of the kinetic solubility in THF compared to Co(XantPhos)Cl 2 , preserving high catalytic productivity upon the addition of LiCl. This allowed the latter to be efficiently used in combination with LiCl as the catalyst for arylzinc compound formation on a 2 g scale. The data obtained in this work can be regarded as experimental confirmation of the first and last stages of the plausible reaction pathway of arylzinc compound formation, involving Co II → Co I and Co I → Co II transformations, which could be a significant framework for further mechanistic investigations.

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Section: Resultssupporting

confidence: 90%

Redox Behavior of Cobalt–Phosphine Complexes vs Their Catalytic Activity in Organozinc Compound Formation: Background for Mechanistic Investigations

et al. 2023

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“…The anodic generation of the electrophile proceeds at +0.5 to +1.5 V (vs. Ag/AgNO 3 , 0.01 M ). The formation of various phosphorus oxyacids and organic phosphorus derivatives, mainly phosphates, pyrophosphates and phosphites, is the result of this cooperative action of electrophilic and nucleophilic reagents generated under electrochemical conditions 20. A series of US patents report the electrochemical synthesis of organophosphorus compounds produced in same synthetic way 21,22.…”

Section: Electrochemical Synthesis Of Organophosphorus Compoundsmentioning

confidence: 99%

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃

2013

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Electrochemical methods have become important from the viewpoint of the development and creation of new ecologically safe and resource‐saving chemical processes. The use of electrons as a “universal” and “inexhaustible” reagent for chemical reactions is the main advantage of electrochemical tools. Although electrochemical processes have been already successfully applied in the preparation of different classes of practically important chemical compounds, a very limited number of industrially applicable electrochemical processes that involve elemental (white) phosphorus is currently known, except for some examples of the electrochemical production of phosphane PH3. These are mainly associated with the investigation of bulk reactions of the electrochemically activated P4 molecule and phosphorus intermediates derived therefrom; very limited attention has been paid to the electrode surface reactions as a key stage of the electrochemical process. In this Microreview we describe the electrode reactions of elemental (white) phosphorus and phosphane that accompany the electrochemical process of the preparation of some phosphorus compounds starting directly from P4. The important role of the nature of the electrode material, the reactivity of the formed phosphorus intermediates and the surface processes are discussed. Moreover, recently, we succeeded in discovering a new, previously unstable phosphorus compound, phosphane oxide H3PO, which can be easily produced using an electrochemical method by mild anodic oxidation of phosphane PH3 electrochemically formed from P4. In this respect, some attention has been paid to the electrochemically induced processes of PH3 oxidation that result in the selective formation of phosphane oxide, which is of high interest from the viewpoint of the investigation of its properties and reactivity.

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“…While the presence of massive photogenerated electron–hole pairs is in vain because of the fast recombination, especially in the heterogeneous photocatalytic system, as expected, there is a dominant pathway that is designed for electron transfer towards the CO 2 molecule via the cobalt complex. 28 After Co II gains an electron, the low valent Co intermediates are stabilized by pyridine ligands through weak coordination, 29 promoting the activation of the CO 2 molecules via nucleophilic attack. The thus formed Co I complexes are important redox active catalysts.…”

Section: Resultsmentioning

confidence: 99%

Improving the photocatalytic reduction of CO₂to CO for TiO₂hollow spheres through hybridization with a cobalt complex

et al. 2018

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Cited by 11 publications

References 6 publications

Redox Behavior of Cobalt–Phosphine Complexes vs Their Catalytic Activity in Organozinc Compound Formation: Background for Mechanistic Investigations

Redox Behavior of Cobalt–Phosphine Complexes vs Their Catalytic Activity in Organozinc Compound Formation: Background for Mechanistic Investigations

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃

Improving the photocatalytic reduction of CO₂to CO for TiO₂hollow spheres through hybridization with a cobalt complex

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Untitled

Cited by 11 publications

References 6 publications

Redox Behavior of Cobalt–Phosphine Complexes vs Their Catalytic Activity in Organozinc Compound Formation: Background for Mechanistic Investigations

Redox Behavior of Cobalt–Phosphine Complexes vs Their Catalytic Activity in Organozinc Compound Formation: Background for Mechanistic Investigations

Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH3

Improving the photocatalytic reduction of CO2to CO for TiO2hollow spheres through hybridization with a cobalt complex

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Electrode Reactions of Elemental (White) Phosphorus and Phosphane PH₃

Improving the photocatalytic reduction of CO₂to CO for TiO₂hollow spheres through hybridization with a cobalt complex