2011

 

Electrochemical synthesis and catalytic activity of organonickel sigma-complexes

Yakhvarov, D.G., Trofimova, E.A., Rizvanov, I.Kh., Fomina, O.S., Sinyashin, O.G.

 

A new industrially applicable method of organonickel sigma-complexes production is developed. The technique is based on the reaction of the oxidative addition of ortho-substituted aromatic bromides to electrochemically generated nickel(0)-2,2′-bipyridyl complexes. Electrolysis is performed in undivided electrolyser supplied with sacrificial nickel anode with a periodic or continuous electrolyte loading. The electrochemically obtained organonickel sigma-complexes of type [NiBr(Ar)(bpy)], where Ar is 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 2,6-dimethylphenyl, are highly effective precatalysts for ethylene oligomerization process, leading to the formation of linear alpha-olefines of C4-C12 fractions.

 

Russian Journal of Electrochemistry, Volume 47, Issue 10, October 2011, Pages 1100-1110

Novel halogen-bridged bisphosphine nickel(II) complexes

Ganushevich, Y., Miluykov, V., Yakhvarov, D., Sinyashin, O., Lönnecke, P., Hey-Hawkins, E. 

 

Reaction of [NiCl2(dtbpe)] (dtbpe = 1,2-bis(di-tert- butylphosphino)ethane) with one equivalent of NaBArF 4 (BArF 4= tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) gives the dinuclear chloro-bridged nickel complex [Ni2(μ-Cl)2(dtbpe)2](BArF 4)2 (1). [Ni(solv)6](BF4)2 reacts with dtbpe to give, depending on the solvent, the fluoro-bridged complex [Ni2(μ-F) 2(dtbpe)2](BF4)2 (2) (solv = THF) or the mononuclear chelate complex [Ni(MeCN)2(dtbpe)](BF 4)2(3) (solv = MeCN). In 1-3, nickel cations are coordinated in a square-planar fashion according to X-ray crystallography. No Ni-Ni interaction was observed in dinuclear halogen-bridged complexes 1 and 2.

 

Inorganica Chimica Acta, Volume 376, Issue 1, 1 October 2011, Pages 118-122

Selective synthesis of nanosized palladium phosphides from white phosphorus

Kagirov, R.M., Voloshin, A.V., Kadirov, M.K., Nizameev, I.R., Sinyashin, O.G., Yakhvarov, D.G.

 

The reaction of white phosphorus with the palladium(0) complex [Pd 2(dba)3] (dba is dibenzylideneacetone) leads to stable associates [Pd(P4)]n. The coordination polymer obtained is stabilized in a solid state via the formation of nanosized palladium phosphides Pd3P2 and Pd6P with average particle sizes of 140 and 65 nm, respectively.

 

Mendeleev Communications, Volume 21, Issue 4, July 2011, Pages 201-203

Experimental evidence of phosphine oxide generation in solution and trapping by ruthenium complexes

Dmitry Yakhvarov, Maria Caporali, Luca Gonsalvi, Shamil Latypov, Vincenzo Mirabello, Ildar Rizvanov, Oleg Sinyashin, Piero Stoppioni, and Maurizio Peruzzini

 

Phosphine oxide (H3PO), the first defined compound of phosphorus in the oxidation state -1, was obtained in solution by electrochemical methods starting from white phosphorus (see picture). H3PO was characterized by NMR solution spectroscopy as a free molecule and isolated as a ligand in ruthenium(II) complexes following tautomerization to phosphinous acid, H2P(OH).

 

Angewandte Chemie - International Edition, Volume 50, Issue 23, 27 May 2011, Pages 5370-5373

New dinuclear nickel(II) complexes: Synthesis, structure, electrochemical, and magnetic properties

Yakhvarov, D., Trofimova, E., Sinyashin, O., Kataeva, O., Budnikova, Y., Lönnecke, P., Hey-Hawkins, E., Petr, A., 

Krupskaya, Y., Kataev, V., Klingeler, R., Büchner, B.

 

The reaction of [NiBr2(bpy)2] (bpy = 2,2′-bipyridine) with organic phosphinic acids ArP(O)(OH)H [Ar = Ph, 2,4,6-trimethylphenyl (Mes), 9-anthryl (Ant)] leads to the formation of binuclear nickel(II) complexes with bridging ArP(H)O2 - ligands. Crystal structures of the binuclear complexes [Ni2(μ- O2P(H)Ar)2(bpy)4]Br2 (Ar = Ph, Mes, Ant) have been determined. In each structure, the metal ions have distorted octahedral coordination and are doubly bridged by two arylphosphinato ligands. Magnetic susceptibility measurements have shown that these complexes display strong antiferromagnetic coupling between the two nickel atoms at low temperatures, apparently similar to binuclear nickel(II) complexes with bridging carboxylato ligands. Cyclic voltammetry and in situ EPR spectroelectrochemistry show that these complexes can be electrochemically reduced and oxidized with the formation of Ni(I),Ni(0)/Ni(III) derivatives. 

 

Inorganic Chemistry, Volume 50, Issue 10, 16 May 2011, Pages 4553-4558

Synthesis of novel methanofullerenes spiro-coupled with the indolinone fragment and prospects of their use in light-absorbing layers of plastic solar cells

Romanova, I.P. , Shaikhutdinova, G.R., Yusupova, G.G., Bogdanov, A.V., Musin, L.I., Yakhvarov, D.G., Valitov, M.I., Nizameev, I.R., Mironov, V.F., Sinyashin, O.G.

 

A series of novel 2′-oxospiro[cyclopropafullerene-3,3′- indolines] was synthesized. Compounds of this type have a significant potential for use as electron-withdrawing components of light-absorbing layers of solar cells.

 

Russian Chemical Bulletin, Volume 60, Issue 5, May 2011, Pages 867-872

Deoxygenation of some α-dicarbonyl compounds by tris(diethylamino) phosphine in the presence of fullerene C60

Romanova, I.P., Bogdanov, A.V. , Mironov, V.F., Shaikhutdinova, G.R., Larionova, O.A., Latypov, S.K., Balandina, A.A., Yakhvarov, D.G., Gubaidullin, A.T., Saifina, A.F., Sinyashin, O.G.

 

The reactions of such cyclic α-diketones as acenaphthenequinone, aceanthrenequinone, and N-alkylisatins, with hexaethyltriaminophosphine in the presence of the fullerene C60, lead to the formation of methanofullerene derivatives under mild conditions. This process proceeds via deoxygenation of the dicarbonyl compound by the P(III) derivative and is likely to involve the intermediate formation of α-ketocarbenes. The structure of some methanofullerenes has been confirmed by NMR and XRD. The electrochemical behavior of the methanofullerenes was also investigated.

 

Journal of Organic Chemistry, Volume 76, Issue 8, 15 April 2011, Pages 2548-2557

2010

 

Activation and transformation of white phosphorus by palladium(ii) complexes

Kagirov, R.M., Voloshin, A.V., Rizvanov, I.K., Sinyashin, O.G., Yakhvarov, D.G.

 

A reaction of bis(triphenylphosphine)palladium dibromide with white phosphorus in the presence of NaBPh4selectively gives phosphorous acid H3PO3. The mechanism of the formation involves coordination of a white phosphorus molecule, ligand exchange, and hydrolysis of the coordinated P4 molecule in the coordination sphere of palladium.

 

Russian Chemical Bulletin, Volume 59, Issue 6, June 2010, Pages 1116-1118

2009

 

Fullerene C60 as an effective trap of acenaphthenone carbene generated in the reaction of acenaphthenequinone with hexaethyltriaminophosphine

Romanova, I.P. , Bogdanov, A.V., Mironov, V.F., Larionova, O.A., Latypov, S.K., Balandina, A.A., Yakhvarov, D.G., Sinyashin, O.G.

 

The three-component reaction of acenaphthenequinone, fullerene C60 and hexaethyltriaminophosphine leads to the formation of the new methanofullerene - 2-{3'-cyclopropa[1,9](C60-Ih)[5,6]fulleren-3'-yl}-1-acenaphthenone.

 

Mendeleev Communications, Volume 19, Issue 6, November 2009, Pages 306-308

New aspects of the electroreduction of palladium dichloride complex with 1,2-bis(diphenylphosphino)ethane

Yakhvarov, D.G., Kagirov, R.M., Rizvanov, I.Kh., Morozov, V.I., Sinyashin, O.G. 

 

The electrochemical reduction of a mono-chelate palladium dichloride complex with 1,2-bis(diphenylphosphino)ethane (dppe) in DMF results in formation of highly reactive mono-chelate palladium(0) complex, which reacts with initial complex by reaction of the ligand abstraction forming stable bischelate complex [Pd0(dppe)2] and palladium dichloride.

 

Mendeleev Communications, Volume 19, Issue 4, July 2009, Pages 190-192

O-Acylated 2-Phosphanylphenol Derivatives - Useful ligands in the Nickel- Catalyzed polymerization of ethylene

Yakhvarov, D.G., Basvani, K.R., Khiderniann, M.K., Dobrynin, A.B., Litvinov, I.A., Sinyashin, O.G., Jones, P.G., Heinicke, J.

 

KhiderThe title ligands were prepared by O-acylation of 2-di- phenylphosphanyl-4-methylphenol (1) or directly by double lithiation of 2-bromo-4-methylphenol and stepwise coupling with ClPPh 2 and ClP(O)Ph 2 or RC(O))C1 (R = Me, tBu, Ph, 4-MeOC 6H 4) to afford diphenylphosphinate 2 and carboxylic esters 3a-d. X-ray crystal structure analyses of 3b-d show conformations in which the P-phenyl substituents are rotated away from the ester group and the C(O)O π planes are nearly perpendicular to the phenol ring π plane. O-Acylated phosphanylphenols 2 and 3a-d form highly active catalysts with Ni(l,5-cod) 2 (as does 1) for polymerization of ethylene, whereas phosphanylphenyl ethers do not give catalysts under the same conditions. The reason is the cleavage of the O-acyl bond upon heating with nickel(O) precursor compounds in the presence of ethylene. The precursors are P- coordinated Ni 0complexes, which are formed at room temperature, such as 4d obtained from 3d and Ni(cod) 2 in a 2:1(molar ratio), and characterized by multinuclear NMR spectroscopy. Upon heating in the presence of ethylene, the pre-catalysts are activated. Catalysts2 Ni and 3a-d Ni convert ethylene nearly quantitatively, 2 Ni slowly, and 3a-d Ni rapidly, into linear polyethylene with vinyl and methyl end groups, and in the latter case, C(O)R end groups are also detectable. This proves insertion of Ni 0into the O-C(O)R bond of 3a-d ligands for formation of the primary catalyst. Termination of the first chain growing cycle by β-hydride elimination changes the mechanism to the phosphanylphenolate- NiH initiated polymerization providing the main body of the polymer. A small retardation in the ethylene consumption rate with 3a-d Ni, catalysts relative to that observed for l Ni and stabilization of the catalyst, which gives rise to reproducibly high ethylene conversion, is observed.

 

European Journal of Inorganic Chemistry, Issue 9, March 2009, Pages 1234-1242

Electrochemical reduction of ZnBr2 in the presence of organic halides

Yakhvarov, D.G., Ganushevich, Yu.S., Dobrynin, A.B., Krivolapov, D.B., Litvinov, I.A., Sinyashin, O.G.

 

Electrochemical reduction of zinc bromide in dimethylformamide, acetonitrile, and tetrahydrofuran in the presence of organic halides (RX) results in the formation of organozinc compounds by oxidative addition of RX to electrochemically generated Zn(0). Effects of the solvent and the nature of organic halides on the electrochemical reduction of zinc (II) ions are analyzed. 

 

Russian Journal of Electrochemistry, Volume 45, Issue 2, February 2009, Pages 139-144

2008

 

Heterobimetallic cooperation mediates the transformation of white phosphorus into zwitterionic catena-phosphonium(+)diphosphenide(-) ligands

Caporali, M., Barbaro, P., Gonsalvi, L., Ienco, A., Yakhvarov, D., Peruzzini, M.

 

White phosphorus is sequentially activated and functionalized by stepwise reaction with cobalt and platinum metal complexes. The two zwitterionic diphenyl(alkyl)phosphonium(+) diphosphenide(-) molecules generated act as bridging side-on/end-on ligands that tether two different metalunits (see picture of the complex core: C black, Co pale green, P orange, Pt green).

 

Angewandte Chemie - International Edition, Volume 47, Issue 20, 5 May 2008, Pages 3766-3768

Bimetallic activation of white phosphorus

Yakhvarov, D., Peruzzini, M., Caporali, M., Gonsalvi, L., Midollini, S., Orlandini, A., Ganushevich, Y., Sinyashin, O.

 

The formation of novel complexes [M(dppm)(Ph2PCH2PPh2PPPP)]OTf (M = Rh, Ir, dppm = bisdiphenylphoshinomethane, OTf = OSO2CF3) bearing in their coordination sphere a new type of oligophosphorus ligands results from bimetallic activation and consequent transformation of white phosphorus. These complexes display electrophilic properties and can be activated either electrochemically or by interaction with nucleophilic reagents.

 

Phosphorus, Sulfur and Silicon and the Related Elements, Volume 183, Issue 2-3, February 2008, Pages 487-493

2007

 

Synthesis of the individual regioisomer of the bisadduct of fullerene C60 with tert-butyl 11-azido-3,6,9-trioxaundecanoate

Romanova, I.P., Yusupova, G.G., Balandina, A.A., Latypov, Sh.K., Yakhvarov, D.G., Nifant'Ev, N.E., Yashunskii, D.V., Sinyashina, O.G.

 

At 130 °C the reaction of fullerene C60 with 1-azido-9-tert-butoxycarbonyl-3,6,9-trioxanonane occurs regioselectively affording one regioisomer of the bisadduct.

 

Russian Chemical Bulletin, Volume 56, Issue 8, August 2007, Pages 1495-1500

Electrocatalytic reduction of aryldichlorophosphines with the (2,2'-bipyridine)nickel complexes

Yakhvarov, D.G., Hey-Hawkins, E., Kagirov, R.M., Budnikova, Yu.H., Ganushevich, Yu.S., Sinyashin, O.G.

 

The reduction of aryldichlorophosphines in organic solvents was studied by cyclic voltammetry, preparative electrolysis, and chemical reduction. The reaction of the electro- chemically generated (2,2';-bipyridine)nickel(0) complexes with aryldichlorophosphines PhPCl2 and tippPCl2 (tipp is 2,4,6-triisopropylphenyl) proceeds through the formation of highly reactive organophosphorus intermediates, whose reactions with diphenylacetylene and hex-1-ene afford phosphirene and phosphirane heterocycles, respectively.

 

 

Russian Chemical Bulletin, Volume 56, Issue 5, May 2007, Pages 935-942

Direct formation of P-C and P-H bonds by reactions of organozinc reagents with white phosphorus

Yakhvarov, D.G., Ganushevich, Y.S., Sinyashin, O.G.

 

Mendeleev Communications, Volume 17, Issue 4, July/August 2007, Pages 197-198

2006

 

A snapshot of P4 tetrahedron opening: Rh- and Ir-mediated activation of white phosphorus

Yakhvarov, D., Barbaro, P., Gonsalvi, L., Carpio, S.M., Midollini, S., Orlandini, A., Peruzzini, M., Sinyashin, O., Zanobini, F.

 

White phosphorus reacts with [M(dppm)2]OTf (M = Rh, Ir; dppm = PPh2CH 2PPh2) to give [M(dppm)-(Ph2PCH 2PPh2PPPP)]OTf whereby a tri-hapto "P 5" ligand is assembled through P-P bond formation between one dppm PPh2 group and an activated P4 molecule (see scheme; P green, M red, C white, phenyl groups omitted). A bimetallic reaction pathway leading to the final product is proposed, as based on in situ 31P NMR studies.

 

Angewandte Chemie - International Edition, Volume 45, Issue 25, 19 June 2006, Pages 4182-4185

Electrochemical synthesis of the σ-aryl complex [NiBr(Mes)(bpy)] and its use as catalyst precursor for the oligomerization of ethylene (Mes = 2,4,6-trimethylphenyl, bpy = 2,2′-bipyridine)

Yakhvarov, D.G., Tazeev, D.I., Sinyashin, O.G., Giambastiani, G., Bianchini, C., Segarra, A.M., Lönnecke, P., Hey-Hawkins, E.

 

The oxidative addition of mesityl bromide either to electrochemically generated [Ni(bpy)] or to [Ni(COD)2] (COD = 1,5-cyclooctadiene) in the presence of 2,2′-bipyridine allows the selective, high-yield synthesis of the σ-aryl complex [NiBr(Mes)(bpy)] (Mes = 2,4,6-trimethylphenyl, bpy = 2,2′-bipyridine), which is an efficient catalyst precursor for the oligomerization of ethylene to even-numbered olefins in the C4-C26 range with a Schulz-Flory distribution.

 

Polyhedron, Volume 25, Issue 7, 8 May 2006, Pages 1607-1612

Synthesis and electrochemical properties of individual isomers of isocyanurate-substituted bis-organodiazadihomofullerenes

Romanova, I.P., Yusupova, G.G., Larionova, O.A., Balandina, A.A., Latypov, Sh.K., Yakhvarov, D.G., Zverev, V.V., Sinyashin, O.G.

 

The reactions of fullerene C60 with isocyanurate-substituted azides afforded individual regioisomers of bis-adducts. The structures of the regioisomers depend on the structure of the organic fragment in azide and are determined primarily by the bulkiness of this fragment. 

 

Russian Chemical Bulletin, Volume 55, Issue 4, April 2006, Pages 697-702

Synthesis, electrochemical properties, and thermal transformations of 1-(5-nitropyrimidin-2-yl)[60]fullereno[1,2-b]aziridine

Romanova, I.P., Yusupova, G.G., Larionova, O.A., Balandina, A.A., Latypov, Sh.K., Zverev, V.V., Yakhvarov, D.G., Rusinov, G.L., Sinyashin, O.G.

 

The reaction of fullerene C60 with 2-azido-5-nitropyrimidine afforded 1-(5-nitropyrimidin-2-yl)[60]fullereno[1,2-b]aziridine, whose electrochemical reduction proceeds more easily than the reduction of nonmodified C60. 

 

Russian Chemical Bulletin, Volume 55, Issue 3, March 2006, Pages 502-506

Synthesis and unusual electrochemical properties of nitropyrimidine- substituted diazadihomo(C60-Ih)[6,6]fullerene

Romanova, I.P. , Yusupova, G.G., Larionova, O.A., Nafikova, A.A., Yakhvarov, D.G., Zverev, V.V., Efremov, Y.Ya., Sinyashin, O.G.

 

A bisadduct regioisomer with two open transannular [6,6]-bonds was synthesised by the cycloaddition reaction of C60 and 2-azido-5-nitropyrimidine.

 

Mendeleev Communications, Issue 6, November/December 2006, Pages 309-311

2005

 

Electrocatalytic eco-efficient functionalization of white phosphorus

Budnikova, Y.H., Yakhvarov, D.G., Sinyashin, O.G.

 

The novel eco-efficient methods to transform white phosphorus into the esters of phosphoric, phosphorous and phosphonic acids, tertiary phosphines and other organophosphorus compounds under conditions of electrochemical catalysis were elaborated. The mechanism of these processes was investigated using the method of cyclic voltammetry and preparative electrolysis.

 

Journal of Organometallic Chemistry, Volume 690, Issue 10, 16 May 2005, Pages 2416-2425

Synthesis and molecular structure of a chiral ferrocenylphosphine

Karasik, A.A., Spiridonova, Y.S., Yakhvarov, D.G., Sinyashin, O.G., Lönnecke, P., Sommer, R., Hey-Hawkins, E.

 

The first chiral (aminomethyl)ferrocenylphosphine (S,S)-1,5-bis(α- methylbenzyl)-3,7-bisferrocenyl-1,5-diaza-3,7-diphosphacyclooctane was obtained via a condensation reaction of bis(hydroxymethyl)ferrocenylphosphine with chiral (S)-α-methyl-benzylamine.

 

Mendeleev Communications, Issue 3, May 2005, Pages 89-90

Activation of white phosphorus in the coordination sphere of nickel complexes with σ-donor ligands

Budnikova, Yu.G., Tazeev, D.I., Kafiyatullina, A.G., Yakhvarov, D.G., Morozov, V.I., Gusarova, N.K., Trofimov, B.A., Sinyashin, O.G.

 

Routes of white phosphorus activation in the coordination sphere of the nickel complexes with different ligands are shown. The first route is based on the coordination of a P4 molecule with the metal, resulting in the deformation of the P4 tetrahedron without destruction. This case is characteristic of the NiX2L complexes, which are reduced at higher cathodic potentials (|Ered| > 0.9 V) (X = BF4, Br, and Cl; L is bpy in DMF, MeCN, and acetone; 2,9-dimethyl-1,10-phenanthroline (phen) and PPh3 in DMF and acetone). To cleave the P-P bonds in the P 4 molecule, this complex should be reduced on the electrode. The second route is the oxidation of white phosphorus in the coordination sphere of the NiII complex. It occurs when the complex has a sufficiently high oxidizing ability and is reduced rather easily (|Ered| < 0.9 V) (X = BF4, L is 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos) in acetone; 1,1′,5,5′-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5- diaza-3,7-diphosphacyclooctane) (n2p2) in DMF; phen and PPh3 in MeCN). The P4 molecule opening is observed to form a new NiI complex containing the (P3) fragment, for example, [(triphos)Ni(P3)Ni(triphos)](BF4)2.

 

Russian Chemical Bulletin, Volume 54, Issue 4, April 2005, Pages 942-947

Synthesis and electrochemical properties of fullerene-containing C 60-acceptor dyads with fluoronitrobenzene and fluoroquinoxaline moieties as substituents

Romanova, I.P., Yusupova, G.G., Larionova, O.A., Yakhvarov, D.G., Mochul'skaya, N.N., Sidorova, L.P., Zverev, V.V., Charushin, V.N., Sinyashin, O.G.

 

Reactions of fullerene C60 with 4-azido-3-fluoro-1-nitrobenzene and 7-azido-6-fluoroquinoxaline afforded earlier unknown cycloadducts (C 60-acceptor dyads), in which the electron affinities of the fullerene spheres are comparable with the affinity of nonmodified C60.

 

Russian Chemical BulletinVolume 54, Issue 3, March 2005, Pages 660-665

2004

 

Heterobimetallic nickel(II) complexes of ferrocenyldithiophosphonates. Molecular structures of [{FcP(OR)S2}2Ni] [Fc = Fe(η5-C5H4)(η5-C 5H5), R = Et, Pri, Bus, Bu i]

Karakus, M., Lönnecke, P., Yakhvarov, D., Hey-Hawkins, E.

 

The reaction of 2,4-diferrocenyl-1,3-dithiadiphosphetane 2,4-disulfide [FcPS(μ-S)]2 [Fc = Fe(η5-C5H 4)(η5-C5H5)] with alcohols ROH gave the corresponding ferrocenyldithiophosphonic acids [FcPS(OR)(SH)], which were treated in situ with Ni(CH3COO)2·4H 2O in acetic acid to yield the square-planar heterobimetallic trinuclear complexes [{FcP(OR)S2}2Ni] (R = Me (1), Et (2), Pri (3), Bus (4) and Bui (5)). Compounds 1-5 were characterized by elemental analysis, MS, NMR (1H, 13C and 31P), IR spectroscopy, and 2-5 also by X-ray crystallography. Cyclovoltammetric studies on the heterobimetallic nickel(II) complexes 1-5 showed irreversible reduction to unstable nickel(I) complexes and an irreversible two-electron oxidation of the sulfur-containing nickel fragments, followed by a reversible one-electron oxidation of the two ferrocenyl groups.

 

Zeitschrift fur Anorganische und Allgemeine ChemieVolume 630, Issue 10, 2004, Pages 1444-1450 

Electrochemical Decomplexation of Phosphine-Pentacarbonyltungsten Complexes: The Phosphole Case

Yakhvarov, D.G., Budnikova, Y.H., Huy, N.H.T., Ricard, L., Mathey, F.

 

Electrochemical reduction of phosphole P-W-(CO) 5 complexes affords the free phospholes in good yields. This technique allows the decomplexation of a 2-ethoxy-4-keto-4,5-dihydrophosphole, which has been characterized by X-ray crystal structure analysis of its P-sulfide.

 

Organometallics, Volume 23, Issue 8, 12 April 2004, Pages 1961-1964

Phosphorylated azahomo[60]fullerene: Synthesis and electrochemical properties

Romanova, I.P., Yusupova, G.G., Nafikova, A.A., Yakhvarov, D.G., Larionova, O.A., Sinyashin, O.G.

 

A reaction of [60]fullerene with O,O-dibutyl azidophosphate affords a first representative of phosphorylated azahomo[60]fullerenes, which is easier to reduce electrochemically than the starting C60.

 

Russian Chemical Bulletin, Volume 53, Issue 1, January 2004, Pages 144-147

2003

 

Reaction of fullerene C60 with 2-azido-4,6-diphenylpyrimidine

Romanova, I.P., Yusupova, G.G., Yakhvarov, D.G., Larionova, O.A., Mochul'skaya, N.N., Sidorova, L.P., Charushin, V.N., Zverev, V.V., Sinyashin, O.G.

 

The first representative of the pyrimidine-substituted [60]fullereno[1,2-b] aziridines was synthesized by the reaction of fullerene C60 with 2-azido-4,6-diphenylpyrimidine. 2-(Azahomo[60]fullereno)-4,6-diphenylpyrimidine was found to be formed as a by-product. The electrochemical properties of the adducts were studied.

 

Russian Chemical Bulletin, Volume 52, Issue 10, October 2003, Pages 2171-2174

Modification of fullerene C60 by phosphorylated diazo compounds

Romanova, I.P., Musina, E.I., Nafikova, A.A., Zverev, V.V., Yakhvarov, D.G., Sinyashin, O.G. 

 

New representatives of phosphorylated methanofullerenes were prepared by the reactions of [60]fullerene with O,O-diethyl α-diazoethyl- and O,O-diethyl α-diazobenzylphosphonates. Electrochemical reduction of the above-mentioned products proceeded stepwise and reversibly.

 

Russian Chemical Bulletin, Volume 52, Issue 8, August 2003, Pages 1750-1757

Kinetic features of oxidative addition of organic halides to the organonickel σ-complex

Yakhvarov, D.G., Budnikova, Yu.H. , Sinyashin, O.G.

 

Electrochemically generated organonickel σ-complexes were used as model compounds to study the kinetics of oxidative addition of ArNi Ibpy to RX, the key stage of cross-coupling of organic halides (RX). The reaction rate constants were calculated, and the sequence of relative reactivity of RX toward the electrochemically generated MesNiIbpy complex was obtained.

 

Russian Chemical Bulletin, Volume 52, Issue 3, March 2003, Pages 567-569

Reactions of [60]fullerene with 2-azidopyrimidines

Romanova, I.P., Kalinin, V.V., Nafikova, A.A., Yakhvarov, D.G., Zverev, V.V., Kovalenko, V.I., Rusinov, G.L., Plekhanov, P.V., Charushin, V.N., Sinyashin, O.G.

 

The reaction of [60]fullerene with 2-azidopyrimidines affords fullerenoimidazopyrimidines, whose electron affinity is higher than that of nonmodified C60.

 

Russian Chemical Bulletin, Volume 52, Issue 1, January 2003, Pages 173-178

Organonickel σ-complexes - Key intermediates of electrocatalytic cycles

Yakhvarov, D.G., Budnikova, Yu.G. , Sinyashin, O.G.

 

Electrochemical reduction of nickel complexes with 2,2′-bipyridyl in the presence of ortho-substituted aromatic bromides or white phosphorus leads to the formation of highly reactive organonickel σ-complexes that are capable of selectively reacting with diverse substrates with the formation of cross-association products. Mechanisms of electrocatalytic processes involving organic halides, chlorophosphines, white phosphorus, and nickel complexes with 2,2′-bipyridyl are studied by the cyclic voltammetry and preparative electrolysis methods. Key intermediates of processes that occur in metallocomplex catalysis are determined.

 

Russian Journal of Electrochemistry, Volume 39, Issue 11, November 2003, Pages 1261-1269

2002

 

Electrochemical reduction of nickel complexes with 2,2′-bipyridine

Budnikova, Yu.G., Yakhvarov, D.G., Morozov, V.I., Kargin, Yu.M., Il'yasov, A.V., Vyakhireva, Yu.N., Sinyashin, O.G.

 

Electrochemical reduction of a nickel complex with 2,2′-bipyridine is accompanied by competing coproportionation yielding paramagnetic Ni I complexes. A decrease in the ligand concentration shifts the equilibrium to the side of the active form of the Ni0bipy catalyst.

 

Russian Journal of General Chemistry, Volume 72, Issue 2, 2002, Pages 168-172

The influence of the sacrificial anode nature on the mechanism of electrochemical arylation and alkylation of white phosphorus

Yakhvarov, D.G., Budnikova, Yu.H., Tazeev, D.I., Sinyashin, O.G.

 

The material of the sacrificial anode has a substantial effect on the nature and yield of the target products of electrochemical phosphorylation of organic halides by white phosphorus in the presence of the nickel complexes with 2,2′-bipyridine. The use of the zinc anode results in the products with tricoordinated phosphorus, viz., triorganylphosphines, the reaction on the aluminum anode affords triorganylphosphine oxides, and the presence of Mg 2+ ions in the reaction mixture provides the transformation of white phosphorus into cyclic phosphines (PhP)5.

 

Russian Chemical Bulletin, Volume 51, Issue 11, 2002, Pages 2059-2064

The reactivity of 2,2′-bipyridine complexes in the electrochemical reduction of organohalides

Yakhvarov, D.G., Samieva, E.G., Tazeev, D.I., Budnikova, Yu.G.

 

Nickel(0) complexes coordinatively unsaturated with 2,2′-bipyridine (bpy) are more reactive in the oxidative addition to organic halides than the saturated analogs, σ-Organonickel complexes formed as intermediates of catalytic cycles were prepared in high yields using nickel complexes coordinatively unsaturated with bpy and aromatic halides containing a methyl group in the ortho-position of the ring.

 

Russian Chemical Bulletin, Volume 51, Issue 5, 2002, Pages 734-741

Synthesis and electrochemical properties of 2-(azahomo[60]fullereno)-5-nitropyrimidine

Romanova, I.P., Kalinin, V.V., Yakhvarov, D.G., Nafikova, A.A., Kovalenko, V.I., Plekhanov, P.V., Rusinov, G.L., Sinyashin, O.G.

 

2-(Azahomo[60]fullereno)-5-nitropyrimidine was synthesised by the cycloaddition reaction of C60 and 2-azido-5-nitropyrimidine.

 

Mendeleev CommunicationsVolume 12, Issue 2, 2002, Pages 51-52

Electrocatalytic reactions involving the NiII- ZnII- 2,2′-bipyridine system

Budnikova, Yu.H., Tazeev, D.I., Yakhvarov, D.G.

 

Factors determining the effect of ZnIIions on the catalytic activity of the NiIIcomplexes with 2,2′-bipyridine (bpy) in the reduction of organohalides were elucidated by cyclic voltammetry and electrolysis. The mechanism proposed involves the reduction of the NiIIbpy complex to Ni0bpy, the oxidative addition of organohalides to the Ni0bpy complex, and nickel transmetallation with the cathode-generated Zn0to form an organozinc compound.

 

Russian Chemical Bulletin, Volume 51, Issue 2, 2002, Pages 269-274

Selective monoarylation of phosphorus trichloride by the electrochemically generated organonickel σ-complex MesNiBrbpy

Yakhvarov, D.G., Budnikova, Y.H. , Sinyashin, O.G.

 

The use of the electrochemically generated organonickel σ-complex MesNiBrbpy enables the selective monoarylation of phosphorus trichloride to be achieved under mild conditions.

 

Mendeleev Communications, Volume 12, Issue 5, September/October 2002, Pages 175-176

2001

 

Highly reactive σ-organonickel complexes in electrocatalytic processes

Budnikova, Y.H., Perichon, J., Yakhvarov, D.G., Kargin, Y.M., Sinyashin, O.G.

 

The electrochemical reduction of nickel complexes with 2,2′-bipyridine in the presence of ortho-substituted organic halides or white phosphorus yields the highly reactive σ-organonickel complexes. These complexes selectively react with organic halides forming cross-coupling products. The mechanism of these processes was investigated using the method of cyclic voltammetry and preparative electrolysis. The key intermediates of electrochemical functioning of white phosphorus in conditions of metallocomplex catalysis were detected.

 

Journal of Organometallic Chemistry, Volume 630, Issue 2, 9 July 2001, Pages 185-192

1998

 

Coordination Catalysis in Organic Electrosynthesis. Electrochemical Reduction of Certain Nickel Subgroup Metal Complexes with Salen Ligands in the Presence of Organic Halides

Budnikova, Yu.G., Yakhvarov, D.G., Kargin, Yu.M.

 

Catalytic activity of electrochemically generated Ni(II) complexes with Salen ligands in dehalogenation reactions is controlled by the electrochemical gap, electronegativity, degree of complex-substrate charge transfer, and also by the stereochemistry of the complex.

 

Russian Journal of General Chemistry, Volume 68, Issue 7, July 1998, Pages 1071-1075