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.

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.

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


Platinum-catalyzed hydrosilylation in polymer chemistry

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

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


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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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

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