2021

Chemical Functionalization of 2D Black Phosphorus toward Its Applications in Energy Devices and Catalysis: A Review

Kuchkaev A.M., Lavate S.Kuchkaev A.MSukhov A.V.Srivastava R.Yakhvarov D.G.

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Due to its unique in-plane anisotropic structure, high carrier mobility, and adjustable direct bandgap, 2D black phosphorus (BP) has emerged as an important graphene-like material for various micro- and optoelectronic, energy, catalytic, and biomedical applications. However, its lack of environmental stability severely limits its processing in ambient conditions. Chemical functionalization is an effective method for increasing the ambient stability of the material. Herein, the main approaches for chemical functionalization of 2D BP with various organic and inorganic substrates, as well as the routes for the preparation of 0D/2D and 2D/2D heterostructures, are discussed. Furthermore, the recent advances of 2D BP-based materials in energy and catalysis fields are summarized. Finally, the challenges and future prospects for the preparation and functionalization of 2D BP are also highlighted. © 2021 Wiley-VCH GmbH

Energy Technology, Volume 9, Issue12, December 2021, № 2100581

Benzothiazole- vs. pyrazole-based unsymmetrical (PCN) pincer complexes of nickel(II) as homogeneous catalysts in ethylene oligomerization

Gafurov Z.N, Zueva E.M., Bekmukhamedov G.E., Kagilev A.A., Kantyukov A.O., Mikhailov I.K., Khayarov K.R., Petrova M.M., Dovzhenko A.P., Rossin A., Giambastiani G., Yakhvarov D.G.

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The nickel complexes (BzTzPCN)NiX (BzTzPC(H)N = 2-(3-((di-tert-butylphosphino)methyl)phenoxy)benzo[d]thiazole; X = F, Br) containing the unsymmetrical pincer k3-tridendate ligand with an oxo-bridged benzothiazole side-arm have been tested as homogeneous catalysts in ethylene oligomerization after preliminary activation by Modified Methylaluminoxane (MMAO). They showed high activity in the process (up to 200 × 103 molC2H4⋅molNi−1⋅h−1), with formation of even-numbered olefins (mainly C4-C10 fractions) as products. The comparison of their performance with the results obtained for more rigid pyrazole-based analogues (PyrPCN)NiX (PyrPC(H)N = 1-[3-[(di-tert-butylphosphino)methyl]phenyl]-1H-pyrazole; X = F, Br) demonstrates a positive effect stemming from the increased ligand flexibility. Moreover, the activation of (BzTzPCN)NiX by MMAO was studied by UV–Vis and 31P NMR spectroscopies combined with time-dependent density functional theory (TD-DFT), revealing the formation of Ni–CH3 species. Finally, DFT calculations were also performed to explore the mechanism of ethylene oligomerization catalyzed by the methyl analogues (PyrPCN)Ni(CH3) and (BzTzPCN)Ni(CH3). © 2021 Elsevier B.V.

Journal of Organometallic Chemistry, Volume 949, 15 September 2021, № 121951

Electrochemical methods for synthesis and in situ generation of organometallic compounds

Gafurov Z.N.Kantyukov A.O.Kagilev A.A.Sinyashin O.G.Yakhvarov D.G.

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The electrochemical methods have a huge synthetic potential in both academia and industry. However, the implementation of electrochemistry for the synthesis of organometallic compounds is presented limitedly, while the sustainability and greenness of the electrochemical protocols allow considering them as a very promising and intriguing approach. This review summarizes the most important and practically useful advances in the electrochemistry of organometallics with the emphases on the direct electrochemical synthesis of organometallic derivatives by the formation of a carbon–metal bond, electrosynthesis of organic compounds mediated by in situ generated organometallics as well as cyclic voltammetry and related techniques, applied for analysis and preparation of organometallic compounds. © 2021 Elsevier B.V.

Coordination Chemistry Reviews, Volume 442, 1 September 2021, № 213986

Nickel Complexes in C‒P Bond Formation

Zagidullin A.A., Sakhapov I.F., Miluykov V.A., Yakhvarov D.G.

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This review is a comprehensive account of reactions with the participation of nickel complexes that result in the formation of carbon–phosphorus (C‒P) bonds. The catalytic and non-catalytic reactions with the participation of nickel complexes as the catalysts and the reagents are described. The various classes of starting compounds and the products formed are discussed individually. The several putative mechanisms of the nickel catalysed reactions are also included, thereby providing insights into both the synthetic and the mechanistic aspects of this phosphorus chemistry. © 2021 by the authors.

Molecules, Volume 26, Issue 17, 31 August 2021, № 5283

Preparation of Cobalt Nanoparticles

Khusnuriyalova A.F.Caporali M.Hey-Hawkins E.Sinyashin O.G.Yakhvarov D.G.

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The various practically useful chemical and physical properties of cobalt nanoparticles (Co NPs) attract a huge interest from the specialists working in different research and industrial fields. However, the selective preparation of Co NPs is a difficult task that requires special conditions and apparatus. This minireview summarises the most successful and useful methods for obtaining Co NPs, including the relevant chemical and physical aspects. © 2021 by the authors.

European Journal of Inorganic Chemistry, Volume 2021, Issue 30, 13 August 2021, Pages 3023-3047

Effect of cation structure on the formation of hydrogen bond between ionic liquids and solute molecules
 
Khachatrian A.A., Rakipov I.T., Mukhametzyanov T.A., Yakhvarov D.G., Solomonov B.N.

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In this work, we have studied the thermochemistry of the hydrogen bond formation between ionic liquids and solute molecules. The solution enthalpies of several organic compounds (benzene, acetone, 3-picoline dimethylsulfoxide, formamide, N-methylformamide, acetamide, N-methylacetamide) in the series of ionic liquids with common anion bis(trifluoromethanesulfonyl)imide and different cations (1-butyl-3-methylimidazolium [BMIM][NTf2], 1-butyl-1-methylpyrrolidinium [BMPYR][NTf2], 1-butylpyridinium [BPY][NTf2], 1-butyl-1-methylpiperidinium [BMPIP][NTf2], trimethylpropylammonium [TMPAm][NTf2]) were measured by solution calorimetry at infinite dilution. The enthalpies of hydrogen bond between solutes and ionic liquids were determined by the previously proposed approach. The hydrogen bond enthalpies were correlated with the proton acceptor ability of ionic liquids from the Kamlet-Abboud-Taft equation and the proton donor ability of amides from the Abraham model. The proton donor ability and hydrogen bond reorganization of studied ionic liquids was analyzed. The formation of the hydrogen bond complexes of linear amides with ionic liquids with different compositions was shown. The effect of the ionic liquid structure on the strength of the hydrogen bond of linear amides with ionic liquids has been established. © 2021 Elsevier B.V.

Journal of Molecular Liquids, Volume 334, 15 July 2021, № 116089

Recent advances in chemistry of unsymmetrical phosphorus-based pincer nickel complexes: From design to catalytic applications

Gafurov, Z.N., Kantyukov A.O.Kagilev A.A.Kagileva A.A.Sakhapov I.F.Mikhailov I.K., Yakhvarov D.G.

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Pincer complexes play an important role in organometallic chemistry; in particular, their use as homogeneous catalysts for organic transformations has increased dramatically in recent years. The high catalytic activity of such bis-cyclometallic complexes is associated with the easy tunability of their properties. Moreover, the phosphorus-based unsymmetrical pincers showed higher catalytic activity than the corresponding symmetrical analogues in several catalytic reactions. However, in modern literature, an increasing interest in the development of catalysts based on non-precious metals is observed. For example, nickel, which is an affordable and sustainable analogue of platinum and palladium, known for its low toxicity, has attracted increasing attention in the catalytic chemistry of transition metals in recent years. Thus, this mini-review is devoted to the recent advances in the chemistry of unsymmetrical phosphorus-based pincer nickel complexes, including the ligand design, the synthesis of nickel complexes and their catalytic applications. © 2021 by the authors.

Molecules, Volume 26, Issue 13, 2 July 2021, № 4063

The role of organonickel reagents in organophosphorus chemistry

Gafurov, Z.N.Kagilev, A.A.Kantyukov, A.O.Sinyashin, O.G.Yakhvarov, D.G.

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Organonickel reagents are widely used for the obtaining of the organophosphorus compounds from different phosphorus sources including elemental white phosphorus, phosphorus trichloride and phosphine PH3. In particular, new highly efficient and environmentally friendly methods for preparation of organophosphorus compounds bearing phosphorus–carbon bonds have been elaborated using the electrochemically generated organonickel complexes. The synthetic application of the developed techniques towards the formation of wide range of practically important primary, secondary and tertiary organophosphines, with a special focus on unsymmetrical PH phosphines, is disclosed. The mechanistic pathways and the structure of the assumed intermediates formed on some key stages of the overall process are presented for discussion. The elaborated methods operate on the electrochemical techniques with combination of coordination chemistry principles and are considered as an efficient alternative to the more common methods. © 2021 Elsevier B.V.

Coordination Chemistry Reviews, Volume 438, 1 July 2021, № 213889

Sustainable Synthesis, NMR and Computational Study of Isobutylmesitylphosphine

Gafurov, Z.N.Zueva, E.M.Yakhvarov, D.G.

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The alkyl-aryl-substituted secondary phosphines i-Bu(Mes)PH and Cy(Mes)PH are obtained from the reaction of the electrochemically generated organonickel sigma-complex [NiBr(Mes)(bpy)] (Mes=2,4,6-trimethylphenyl; bpy=2,2′-bipyridine) with primary phosphines i-BuPH2 and CyPH2, respectively. Detailed multinuclear NMR spectroscopy and quantum-chemical calculations were used to assign the diastereotopic protons of i-Bu(Mes)PH. © 2021 Wiley-VCH GmbH

ChemistrySelect, Volume 6, Issue 8, 24 February 2021, Pages 1833-1837

Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {Mo3PdS4}

Kuchkaev, A.M.Shmelev, N.Y.Kuchkaev, A.M.Sukhov, A.V.Babaev, V.M.Khayarov, K.R.Gushchin, A.L.Sokolov, M.N.

Sinyashin, O.G.Yakhvarov, D.G.

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Reaction of heterometallic cubane-type cluster complexes-[Mo3{Pd(dba)}S4Cl3(dbbpy)3]PF6, [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl and [Mo3{Pd(dba)}S4(acac)3(py)3]PF6, where dba-dibenzylideneacetone, dbbpy-4,4'-di-tert-butyl-2,2'-bipyridine, tu-thiourea, acac-acetylacetonate, py-pyridine, with white phosphorus (P4) in the presence of water leads to the formation of phosphorous acid H3PO3 as the major product. The crucial role of the Pd atom in the cluster core {Mo3PdS4} has been established in the hydrolytic activation of P4 molecule. The main intermediate of the process, the cluster complex [Mo3{PdP(OH)3}S4Cl3(dbbpy)3]+ with coordinated P(OH)3 molecule and phosphine PH3, have been detected by 31P NMR spectroscopy in the reaction mixture. © 2020 by the authors.

Molecules, Volume 26, Issue 3, 21 January 2021, № 538

Group additive approach for heterocyclic aromatic solutes in [BMIM][BF4]

Khachatrian, A.A.Yakhvarov, D.G.Sinyashin, O.G.Rakipov, I.T.Mukhametzyanov, T.A.Solomonov, B.N.

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This work continues the development of the additive scheme for the calculation of solvation enthalpies of aromatic compounds in 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]). In this study, heterocyclic aromatic compound were selected as solutes. The solution enthalpies of 14 heterocyclic aromatic compounds in [BMIM][BF4] were measured at 298.15 K. Based on the experimental and literature data, the solvation enthalpies of heterocyclic aromatic compounds in [BMIM][BF4] were calculated. The contributions of the exchange of CH–group with –N=, >NH, >NCH3, –S–, and carbonyl >C=O substituent groups into the solvation enthalpies in [BMIM][BF4] were calculated. These values were compared with analogous contributions in benzene. Solvation enthalpies of heterocyclic aromatic compounds in [BMIM][BF4] calculated by the additive scheme were compared with experimental values, revealing a good agreement between calculated and experimental data. This fact indicates that group additive scheme for prediction of the solvation enthalpies can be successfully applied to heterocyclic aromatic compounds in ionic liquids. © 2020 Elsevier B.V.

Journal of Molecular Liquids,Volume 321, 1 January 2021, № 114746

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By methods of cyclic voltammetry and preparative electrolysis, the electrochemical properties ofsterically  hindered  imidazolium  salt  3-(6-(1H-pyrazol-1-yl)pyridin-2-yl)-1-(2,6-diisopropylphenyl)-1H-imidazol-3-ium bromide containing the pyrazolyl-pyridyl moiety are studied and the N-heterocyclic carbenecomplexes of nickel(II) are electrochemically synthesized by the cathodic reduction of this salt in the pres-ence of nickel(II) ions. The monitoring of this preparative electrosynthesis by mass spectrometric measure-ments  demonstrates  that  these  organonickel  complexes  can  contain  either  one  (when  a  diaphragm  cell  isused) or two (when the diaphragmless cell contains a soluble nickel anode) N-heterocyclic carbene ligands. © 2020 by the authors.

Russian Journal of Electrochemistry, Vol. 57, No. 2, 2021, P. 134–140.

2020

Platinum-catalyzed hydrosilylation in polymer chemistry

Lukin, R.Y.Kuchkaev, A.M.Sukhov, A.V.Bekmukhamedov, G.E.Yakhvarov, D.G.

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This paper addresses a review of platinum-based hydrosilylation catalysts. The main field of application of these catalysts is the curing of silicone polymers. Since the 1960s, this area has developed rapidly in connection with the emergence of new polymer compositions and new areas of application. Here we describe general mechanisms of the catalyst activity and the structural effects of the ligands on activity and stability of the catalysts together with the methods for their synthesis. © 2020 by the authors.

Polymers, Volume 12, Issue 10, October 2020, № 2174

2020

Hydrogen bonding of linear and cyclic amides in ionic liquids

Khachatrian, A.A.Yakhvarov, D.G., Sinyashin, O.G.Rakipov, I.T.Mukhametzyanov, T.A.Solomonov, B.N.

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The present work focuses on hydrogen bonding of linear and cyclic amides (formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, 2-pyrrolidone) in several ionic liquid (1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [BMIM][NTf2], 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4], 1-butyl-3-methylimidazolium trifluoromethanesulfonate [BMIM][TfO], 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], triethylsulfonium bis(trifluoromethylsulfonyl)imide [Et3S][NTf2], Trimethylpropylammonium bis(trifluoromethylsulfonyl)imide [TMPAm][NTf2]). The solution enthalpies of amides in ionic liquids were measured by solution calorimetry at infinite dilution. The hydrogen bond enthalpies were calculated based on solution enthalpies of amides in ionic liquids. The hydrogen bond enthalpies of linear and cyclic amides in ionic liquids and organic proton acceptors were compared. The influence of active proton donor center on the formation of hydrogen bond complexes between amides and ionic liquids was analyzed. © 2020 Elsevier B.V.

Thermochimica Acta, Volume 692, October 2020, № 178757

The formation of mesitylphosphine and dimesitylphosphine in the reaction of organonickel σ-complex [NiBr(Mes)(bpy)] (Mes = 2,4,6-trimethylphenyl, bpy = 2,2′-bipyridine) with phosphine PH3

Gafurov, Z.N.Sakhapov, I.F.Kagilev, A.A.Kantyukov, A.O.Khayarov, K.R.Sinyashin, O.G.Yakhvarov, D.G.

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The reactivity of the previously reported organonickel σ-complex [NiBr(Mes)(bpy)], where Mes = 2,4,6-trimethylphenyl, bpy = 2,2′-bipyridine, toward phosphine PH3 was investigated. The reaction leads to primary mesitylphosphine MesPH2 as the main product and dimesitylphosphine Mes2PH as secondary product with the nickel complex as transmetalating agent. The formed MesPH2 reacts with an excess of the complex giving Mes2PH as the major product. © 2020, © 2020 Taylor & Francis Group, LLC.

Phosphorus, Sulfur and Silicon and the Related Elements, Volume 195, Issue 9, 1 September 2020, Pages 726-729

The effect of N-substituent on the relative thermodynamic stability of unionized and zwitterionic forms of α-diphenylphosphino-α-amino acids

Soficheva, O.S.Nesterova, A.A.Dobrynin, A.B.Zueva, E.M., Heinicke, J.W.Sinyashin, O.G.Yakhvarov, D.G.

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The relative thermodynamic stability of unionized and zwitterionic forms of α-phosphino-α-amino acids is governed by the substituent R at the nitrogen atom, namely, (het)aryl substituents favour the formation of the unionized form RHNCH(PPh2)COOH, while in the case of alkyl analogues the zwitterions RH2N+CH(PPh2)COO− predominate. The experimentally observed trends have been supported by quantum-chemical calculations. The synthesis and X-ray crystal structure analysis of a new unionized α-phosphino-α-amino acid [α-diphenylphosphino-N-(2-methoxycarbonylphenyl) glycine] are reported. © 2020

Mendeleev Communications, Volume 30, Issue 4, July - August 2020, Pages 516-518

CO2 electrochemical reduction by exohedral N-pyridine decorated metal-free carbon nanotubes

Tuci, G.Filippi, J.Rossin, A.Luconi, L.Pham-Huu, C.Yakhvarov, D.G.Vizza, F.Giambastiani, G.

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Electrochemical CO2 reduction reaction (CO2RR) to fuels and chemicals represents nowadays one of the most challenging solutions for renewable energy storage and utilization. Among the possible reaction pathways, CO2-to-CO conversion is the first (2e-) reduction step towards the production of a key-feedstock that holds great relevance for chemical industry. In this report we describe the electrocatalytic CO2-to-CO reduction by a series of tailored N-decorated carbon nanotubes to be employed as chemoselective metal-free electrocatalysts. The choice of an exohedral functionalization tool for the introduction of defined N-groups at the outer surface of carbon nanomaterials warrants a unique control on N-configuration and electronic charge density distribution at the dangling heterocycles. A comparative electrochemical screening of variably N-substituted carbon nanomaterials in CO2RR together with an analysis of the electronic charge density distribution at each heterocycle have suggested the existence of a coherent descriptor for the catalyst's CO faradaic efficiency (FECO). Evidence allows to infer that N-configuration (N-pyridinic vs. N-pyrrolic) of exohedral dopants and electronic charge density distribution at the N-neighboring carbon atoms of each heterocycle are directly engaged in the activation and stabilization of CO2 and its reduction intermediates. © 2020 by the authors.

Energies, Volume 13, Issue 11, June 2020, № 2703

Ni-based complexes in selective ethylene oligomerization processes

Bekmukhamedov, G.E.Sukhov, A.V.Kuchkaev, A.M.Yakhvarov, D.G.

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Linear alpha-olefins are widely used in the petrochemical industry and the world demand for these compounds increases annually. At present, the main method for producing linear alpha-olefins is the homogeneous catalytic ethylene oligomerization. This review presents modern nickel catalysts for this process, mainly systems for obtaining of one of the most demanded oligomer—1-butene—which is used for the production of linear low density polyethylene (LLDPE) and high density polyethylene (HDPE). The dependence of the catalytic performance on the composition and the structure of the used activated complexes, the electronic and coordination states of the nickel center was considered. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.

Catalysts, Volume 10, Issue 5, May 2020, № 498

Electrochemical Properties of N-Substituted α-Diphenylphosphinoglycines

Soficheva, O.S.Kislitsyn, Y.A.Nesterova, A.A.Dobrynin, A.B.Yakhvarov, D.G.

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The electrochemical properties of the N-substituted α-diphenylphosphinoglycines N-(2-methoxybenzyl) diphenylphosphinoglycine (1), N-(pyrazin-2-yl) diphenylphosphinoglycine (2), N-(1-adamantyl) diphenylphosphinoglycine (3), and N-(2,5-dimethoxycarbonylphenyl) diphenylphosphinoglycine (4) obtained in the three-component condensation of diphenylphosphine, glyoxylic acid hydrate, and the corresponding amine were studied by cyclic voltammetry on a glassy carbon electrode. The structure of compound 4 was confirmed by X-ray diffraction analysis. Compounds 1–4 exhibited electrochemical activity in the anodic region of potentials due to the presence of an oxidizable diphenylphosphine fragment in the molecule. Compound 4 can also be electrochemically reduced at the cathodic potentials of the working electrode due to the ester groups in the aromatic fragment. © 2020, Pleiades Publishing, Ltd.

Russian Journal of Electrochemistry, Volume 56, Issue 5, 1 May 2020, Pages 431-436

Bis(α-hydroxycycloalkyl)phosphine Oxides Obtained from White Phosphorus via Phosphine Oxide H3PO: Synthesis, Molecular Structure, Coordination Properties and Biological Activity

Gorbachuk, E.Badeeva, E.Gubaidullin, A.Samigullina, A.Voloshina, A.Sapunova, A.Hey-Hawkins, E.Sinyashin, O.Yakhvarov, D.

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Reaction of the electrochemically in situ from elemental white phosphorus generated phosphine oxide H3PO in a single electrochemical cell, supplied with lead cathode and aluminium anode, with cyclic ketones (cyclopentanone and cyclohexanone) results in formation of secondary phosphine oxides (bis(α-hydroxycyclopentyl)phosphine oxide 2 a, isolated yield 15 %, and bis(α-hydroxycyclohexyl)phosphine oxide 2 b, isolated yield 12 %) with two α-hydroxycycloalkyl substituents at the phosphorus atom. Bis(α-hydroxycyclopentyl)phosphine oxide reacts with [PdCl2(COD)] (COD=1,5-cyclooctadiene) to give a new palladium complex trans-[PdCl2{P(OH)(cyclo-C5H8-1-OH)2}2] (3 a, isolated yield 11 %) bearing phosphinous acid as a ligand formed via tautomerization of the phosphine oxide. Finally, the cytotoxicity of the synthesized secondary phosphine oxides on tumor and healthy human cell lines was studied. It was found that at a concentration of 10−6–10−4 M, phosphine oxides 2 a,b exhibit similar IC50 values for the M-Hela cell line (ca. 50 mM), but are non-toxic for MCF-7 cells. For human alveolar adenocarcinoma cells (A-549), only 2 a is active (ca. 35 mM), while 2 b is not toxic. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

ChemPlusChem, Volume 85, Issue 5, 1 May 2020, Pages 958-962

Unsymmetrical pyrazole-based PCN pincer NiII halides: Reactivity and catalytic activity in ethylene oligomerization

Gafurov, Z.N.Bekmukhamedov, G.E.Kagilev, A.A.Kantyukov, A.O.Sakhapov, I.F.Mikhailov, I.K.Khayarov, K.R.Zaripov, R.B.,

Islamov, D.R.Usachev, K.S.Luconi, L.Rossin, A.Giambastiani, G.Yakhvarov, D.G.

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The reactivity of unsymmetrical pyrazole-based PCN pincer Ni(II) halides has been tested in the presence of copper(II) halides as an oxidizing agent as well as with NaBH4 and LiAlH4 as a hydride source. While the reaction with CuX2 resulted into the generation of metastable PCN pincer Ni(III) species, the treatment of (tBuPCN)NiCl with NaBH4 led to the preparation and isolation of the borohydride complex (tBuPCN)Ni(BH4). Attempts to isolate nickel-hydride species upon treatment of (tBuPCN)NiCl with either NaBH4 or LiAlH4 invariably led to the formation of free PCN(H) ligand and metallic Ni(0) nanoparticles after an in situ reductive elimination from the (metastable) hydride derivative (tBuPCN)NiH. Finally, the halide complexes (pre-activated by MMAO) have been tested as homogeneous catalysts in ethylene oligomerization showing moderate activity (∼ 14 × 103 molC2H4⋅molNi−1⋅h−1) with the formation of even-numbered olefins (mainly C4–C10 fractions) as products. © 2020 Elsevier B.V.

Journal of Organometallic Chemistry, Volume 912, 15 April 2020, № 121163

Electrochemical Properties of Cobalt(II), Nickel(II) and Iron(II) Ions in the Presence of 2,2'-Bipyridine

Khusnuriyalova, A.F.Sukhov, A.V.Bekmukhamedov, G.E.Yakhvarov, D.G.

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Abstract: The electrochemical properties of cobalt(II), nickel(II), and iron(II) ions are studied by cyclic voltammetry in the presence of increasing amounts of 2,2'-bipyridine (bpy). It is shown that the addition of insignificant amounts of bpy (10–50 mol %) to solutions containing cobalt(II), nickel(II), and iron(II) ions leads to stabilization of the reduced metal(0) forms and prevents both their electrochemical deposition and the formation of unsoluble metal associates. © 2020, Pleiades Publishing, Ltd.

Russian Journal of Electrochemistry, Volume 56, Issue 4, 1 April 2020, Pages 293-299

Unsymmetrical nickel (PCN) pincer complexes with a benzothiazole side-arm: Synthesis, characterization and electrochemical properties

Luconi, L.Tuci, G.Gafurov, Z.N.Mercuri, G.Kagilev, A.A.Pettinari, C.Morozov, V.I.Yakhvarov, D.G.Rossin, A.Giambastiani, G.

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The newly prepared unsymmetrical pincer ligand with a benzothiazole side-arm 2-(3-((di-tert-butylphosphino)methyl)phenoxy)benzo[d]thiazole [BzTz(H)PCN] has been reacted with anhydrous NiBr2 to get the corresponding NiII square planar bromo complex (BzTzPCN)NiBr (1) after HBr elimination and C[sbnd]H activation on the pincer central phenyl ring. Starting from 1, reaction with AgF in toluene or with AgBF4 in THF led to bromide abstraction and formation of the fluoro complex (BzTzPCN)NiF (2) and the ionic aquo species [(BzTzPCN)Ni(H2O)]BF4 (3), respectively. All species have been characterized in solution (multinuclear 1H, 13C{1H}, 31P{1H} and 11B NMR spectroscopy) and in the solid state (single-crystal X-ray diffraction analysis). Finally, comparative electrochemical measurements (CV and in situ EPR-spectroelectrochemistry) carried out on the halide complexes 1 and 2 revealed that the anodic oxidation process leads to the formation of stable NiIII species bearing a coordinated bromide ligand in case of 1 and a fluoride-free complex in case of 2. © 2020

Inorganica Chimica Acta, Volume 517, 1 March 2020, № 120182