Center for Magnetic Resonance

A. Penkova, G. Polotskaya, A. Toikka
“Pervaporation composite membranes for ethyl acetate production”
Chem. Eng. Process., 2014, accepted
DOI: 10.1016/j.cep.2014.11.015

T. Minh Dau, Y.-A. Chen, A.J. Karttunen, E.V. Grachova, S.P. Tunik, K.-T. Lin, W.-Y. Hung, P.-T. Chou, T.A. Pakkanen, I.O. Koshevoy
“Tetragold(I) complexes: solution isomerization and tunable solid-state luminescence”
Inorg. Chem., 2014, accepted

A.I. Solomatina, D.V. Krupenya, V.V. Gurzhiy, I. Zlatkin, A.P. Pushkarev, M.N. Bochkarev, N.A. Besley, E. Bichoutskaia, S.P. Tunik
“Cyclometallated platinum(II) complexes containing NHC ligands; synthesis, characterization, photophysics and their application as emitters in OLEDs”
Dalton Trans., 2014, accepted

First paper of 2015 with acknowledgments to CMR:

M.Ya. Demakova, D.S. Bolotin, N.A. Bokach, G.L. Starova, V.Yu. Kukushkin

“Metal-mediated cyanamide–hydroxyguanidine coupling” Inorg Chim. Acta, 2015, 425, 114-117

DOI: 10.1016/j.ica.2014.10.015

Reaction of the cyanamides R₂NCN (R = Me 2a, Et 2b) with the hydroxyguanidine OC₄H₈NC(=NOH)NH₂ (1) in the presence of zinc halides leads to [ZnX₂{HN=C(NR₂)ON=C(NH₂)NC₄H₈O}] derived from the ZnIImediated cyanamide–hydroxyguanidine coupling. This reaction is the first observation of interplay between any nitrile group and any hydroxyguanidine both in metal-involving and metal-free chemistry. Complexes 3a,b–5a,b rather rapidly degrade in solutions at RT, but solvates 3a,b MeOH and 4a MeOH are sufficiently stable in the solid state and they were characterized by IR, HRESI⁺-MS, solid state CP-MAS TOSS ¹³C NMR, and X-ray crystallography (for 3a,b). Complexes 4b and 5a,b were identified in solutions by HRESI⁺-MS.

A.S. Konev, A.F. Khlebnikov, P.I. Prolubnikov, A.S. Mereshchenko, A.V. Povolotskiy, O.V. Levin, A. Hirsch, “Synthesis of New Porphyrin–Fullerene Dyads Capable of Forming Charge-Separated States on a Microsecond Lifetime Scale”
Chem. Eur. J. 2014, 20, 1-15
DOI: 10.1002/chem.201404435

N.A. Danilkina, A.E. Kulyashova, A.F. Khlebnikov, S. Bräse, I.A. Balova, “Electrophilic Cyclization of Aryldiacetylenes in the Synthesis of Functionalized Enediynes Fused to a Heterocyclic Core”
J. Org. Chem. 2014, 79(19), 9018-9045
DOI: 10.1021/jo501396s

A.F. Khlebnikov, O.A. Tomashenko, L.D. Funt, M.S. Novikov, “Simple Approach to Pyrrolylimidazole Derivatives by Azirine Ring Expansion with Imidazolium Ylides”
Org. Biomol. Chem. 2014, 12, 6598-6609
DOI: 10.1039/c4ob00865k

A.S. Konev, D.A. Lukyanov, P.S. Vlasov, O.V. Levin, A.A. Virtsev, I.M. Kislyakov, A.F. Khlebnikov, “The Implication of 1,3-Dipolar Cycloaddition of Azomethine Ylides to the Synthesis of Main-Chain Porphyrin Oligomers”
Macromol. Chem. Phys. 2014, 215, 516-529
DOI: 10.1002/macp.201300679

P.V. Gushchin, M.L. Kuznetsov, M. Haukka, V.Yu. Kukushkin, “Anionic halide…alcohol clusters in the solid state”
J. Phys. Chem. A 2014, 118,, 9529-9539
DOI: 10.1021/jp506256a

A.F. Khlebnikov, M.S. Novikov, Y.G. Gorbunova, E.E. Galenko, K.I. Mikhailov, V.V. Pakalnis, M.S. Avdontceva “Isoxazolium N-ylides and 1-oxa-5-azahexa-1,3,5-trienes on the way from isoxazoles to 2H-1,3-oxazines”
Beilstein J. Org. Chem. 2014, 10, 1896-1905
DOI: 0.3762/bjoc.10.197

K.V. Zavyalov, M.S. Novikov, A.F. Khlebnikov, V.V. Pakalnis, “Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine ring expansion”
Tetrahedron 2014 2014, 70(21), 3377-3384
DOI: 10.1002/macp.201300679

A.N. Kazakova, R.O. Iakovenko, V.M. Muzalevskiy, I.A. Boyarskaya, M.S. Avdontceva, G.L. Starova, A.V. Vasilyev, V.G. Nenajdenko
“Trifluoromethylated allyl alcohols: acid-promoted reactions with arenes and unusual ‘dimerization’”

Tetrahedron Lett., 2014, 55, 6851-6855

DOI: 10.1016/j.tetlet.2014.10.083

An unusual ‘dimerization’ of CF₃-allyl alcohols [ArCH=CHCH(OH)CF₃] under the action of anhydrous FeCl₃ was found to give fluorinated indanes in 62–90% yields via the formation of intermediate allyl cations. Reactions of CF₃-allyl alcohols with arenes (Ar′H) led to CF₃-alkenes [Ar(Ar′)CHCH=CHCF₃] in 48–75% yields. The mechanisms of the transformations are discussed.

T.B. Anisimova, M. Fátima C. Guedes da Silva, V.Yu. Kukushkin, A.J. L. Pombeiro, K.V. Luzyanin

“Metal-mediated coupling of amino acid esters with isocyanides leading to new chiral acyclic aminocarbene complexes”

Dalton Trans., 2014, 43, 15861-15871

DOI: 10.1039/c4dt01917b

Metal-mediated coupling between equimolar amounts of cis-[PdCl2(CNR1)2] (1–5) and the amino acid esters L-HTyrOMe (7) or L-HProOtBu (8) proceeds at 40 °C in chloroform over ca. 6 h. The subsequent workup affords the complexes cis-[PdCl2(CNR1){C(TyrOMe)[double bond, length as m-dash]NHR1}] (R1 = Xyl 9, 2-Cl-6-Me-C6H310) or cis-[PdCl2(CNR1){C(ProOtBu)[double bond, length as m-dash]NHR1}] (R1 = Xyl 11, 2-Cl-6-Me-C6H312, Cy 13, tBu 14, 2-naphthyl 15) in good to excellent isolated yields (75–94%). The corresponding reaction between trans-[PdI2(CNR1)2] (6) and 8 brings about the formation of trans-[PdI2(CNCy){C(ProOtBu)[double bond, length as m-dash]NHCy}] (16, 76% isolated yield). The reaction of 6 with 7 proceeds non-selectively giving a broad mixture of products. Complexes 9–16 were characterized by elemental analyses (C, H, N), ESI+/−-MS, IR, 1D (1H, 13C{H}) and 2D (1H,1H-COSY, 1H,13C-HMQC/1H,13C-HSQC, 1H,13C-HMBC) NMR spectroscopic techniques, and by single-crystal X-ray diffraction (for 9, 11–13, and 16).

M.Ya. Demakova, K.V. Luzyanin, G.L. Starova, V.Yu. Kukushkin
“Facile alternative route to cis-[PtCl2(PTA)2] and [PtCl(PTA)3]Cl (PTA = 1,3,5-triaza-7-phosphaadamantane)”

Inorg. Chem. Commun., 2014, 50, 17-18

DOI: 10.1016/j.inoche.2014.10.002

The reaction of trans-[PtCl2(Me2SO)2] with 2 equivs of 1,3,5-triaza-7-phosphaadamantane (PTA) in MeNO₂ at RT furnished cis-[PtCl₂(PTA)₂] (1) in 87% isolated yield. Corresponding reaction of K₂[PtCl₄] with 1 equiv. of PTA in aqueous EtOH at RT led to [PtCl(PTA)₃]Cl (2) in 84% isolated yield. Complexes 1 and 2 were characterized by elemental analyses (C, H, N), HR-ESI+/−-MS, IR, ¹H and ³¹P{¹H} NMR spectroscopic techniques, and by single-crystal X-ray diffraction for 1.

D.S. Bolotin, K.I. Kulish, N.A. Bokach, G.L. Starova, V.V. Gurzhiy, V.Yu. Kukushkin

“Zinc(II)-Mediated Nitrile−Amidoxime Coupling Gives New Insights into H+‑Assisted Generation of 1,2,4-Oxadiazoles”

Inorg. Chem., 2014, 53, 10312-10324

DOI: 10.1021/ic501333s

The cyanamides Me₂NCN (1a), OC₄H₈NCN (1b), and PhC(═O)N(H)CN (1c) and the conventional nitriles PhCN (1d) and EtCN (1e) react with 1 equiv of each of the amidoximes R′C(═NOH)NH₂ (R′ = Me (2a), Ph (2b)) in the presence of 1 equiv of ZnCl₂ producing the complexes [ZnCl₂{HN═C(R)ON═C(R′)NH₂}] (R/R′ = NMe₂/Me (3a), NMe₂/Ph (3b), NC₄H₈O/Me (3c), NC₄H₈O/Ph (3d), N(H)C(═O)Ph/Me (3e), N(H)C(═O)Ph/Ph (3f), Ph/Me (3g), Ph/Ph (3h), Et/Ph (3j)) with the chelate ligands originating from the previously unreported zinc(II)-mediated nitrile–amidoxime coupling. Addition of 1 equiv of p-TolSO₃H to any of one 3a–h, 3j results in the ligand liberation and formation of the iminium salts [H₂N═C(R)ON═C(R′)NH₂](p-TolSO₃) ([4a–j](p-TolSO₃)), which then at 20–65 °C spontaneously transform to 1,2,4-oxadiazoles (5a–j). As a side reaction, cyanamide derived species [4a–f](p-TolSO₃) undergo Tiemann rearrangement to produce the substituted ureas R′NHC(═O)NH₂ (R′ = Me (6a), Ph (6b)) and RC(═O)NH₂ (R = NMe₂ (6c), NC₄H₈O (6d), N(H)C(═O)Ph (6e)), whereas phenyl and ethyl cyanide derivatives besides their transformation to the oxadiazoles undergo hydrolysis to the parent amidoxime R′C(═NOH)NH₂ (R′ = Me (2a), Ph (2b)) and the carboxamides RC(═O)NH₂ (R = Ph (6f), Et (6g)). All new obtained compounds were characterized by HRESI-MS, IR, ATR-FTIR, ¹H NMR, CP-MAS TOSS ¹³C NMR, elemental analyses (C, H, N), and single crystal X-ray diffraction for seven species (3a–e, [4b](p-TolSO₃), and [4d](p-TolSO₃)). Two previously unknown heterocycles 5c and 5e were isolated and characterized by elemental analyses (C, H, N), HRESI-MS, IR, ¹H and ¹³C{¹H} NMR. The observed conversion of [4a–j](p-TolSO₃) to the 1,2,4-oxadiazoles uncovers the mechanism of the previously reported H+-assisted generation of these heterocycles (Augustine; et al. J. Org. Chem. 2009, 74, 5640).

S. Miltsov, V. Karavan, M. Goikhman, I. Podeshvo, S. Gómez-de Pedro, M. Puyol, J. Alonso-Chamarro

“Synthesis of bis-aminosubstituted indocyanine dyes for their use in polymeric compositions”

Dyes and Pigments, 2014, 109, 34-41

DOI:10.1016/j.dyepig.2014.05.002

The synthesis of a set of open-chain bis-aminosubstituted cyanine dyes as well as others with cyclic fragments in the polymethine chain is presented. These dyes are suitable for the development of polymeric compositions with variable optical characteristics as they can be covalently incorporated into the polymer.

M.Ya. Goikhmana, N.P. Yevlampieva, I.V. Podeshvo, S.A. Mil’tsov, V.S. Karavan, I.V. Gofman, A.P. Khurchak, A.V. Yakimansky

“Polymers with Cyanine Chromophore Groups in the Main Chain: Synthesis and Properties”

Polymer Science B, 2014, 56, 352-359

DOI:10.1134/S1560090414030051

Polyamides containing fragments of two cyanine chromophores in the main chain are synthesized, and their viscometric and electro-optical properties in solutions, as well as their stress-strain properties in films, are investigated. It is shown that the molecular characteristics of the copolyamides are substantially affected by chromophore fragments at a content of 10 mol %, while the mechanical properties of the films are independent of the chemical structures of chromophores incorporated into polyamide chains

A.S. Smirnov, E.S. Butukhanova, N.A. Bokach, G.L. Starova, V.V. Gurzhiy, M.L. Kuznetsov, V.Yu. Kukushkin

“Novel (cyanamide)ZnII complexes and zinc(II)-mediated hydration of the cyanamide ligands”

Dalton Trans, 2014, 43, 15798-15811

DOI:10.1039/c4dt01812e

The cyanamides NCNR₂ (R₂ = Me₂, Ph₂, C₅H₁₀) react with ZnX₂ (X = Cl, Br, I) in a 2[thin space (1/6-em)]:[thin space (1/6-em)]1 molar ratio at RT, giving a family of zinc(II) complexes [ZnX2(NCNR2)2] (R2 = Me2, X = Cl 1, X = Br 2, X = I 3; R2 = C5H10, X = Cl 4, X = Br 5; X = I 6; R2 = Ph2, X = Cl 7, X = Br 8, X = I 9; 75–92% yields). Complexes 7 and 8 undergo ligand redistribution in wet CH₂Cl₂ solutions giving the [Zn(NCNPh₂)4(H₂O)₂][Zn₂(μ-X)₂X₄] (X = Cl 10, Br 11) species that were characterized by 1H NMR, HRESI-MS, and X-ray diffraction. Halide abstraction from 1–3 by the action of AgCF₃SO₃ or treatment of Zn(CF₃SO₃)₂ with NCNR₂ (R₂ = Me₂, C₅H₁₀) leads to labile complexes [Zn(CF₃SO₃)₂(NCNR₂)₃] (R₂ = Me₂, 12; C₅H₁₀, 13). Crystallization of 12 from wet CH₂Cl₂ or from the reaction mixture gave [Zn(NCNMe₂)₃(H₂O)₂](SO₃CF₃)₂ (12a) or [Zn(CF₃SO₃)₂(NCNMe₂)₂]∞ (12b), whose structures were determined by X-ray diffraction. The ZnII-mediated hydration was observed for the systems comprising ZnX₂ (X = Cl, Br, I), 2 equiv. NCNR2 (R₂ = Me₂, C₅H₁₀, Ph₂) and ca. 40-fold excess of water and conducted in acetone at 60 °C (R₂ = Me₂, C₅H₁₀) or 80 °C (R₂ = Ph₂) in closed vials, and it gives the urea complexes [ZnX₂{OC(NR₂)NH₂}] (R₂ = Me₂, X = Cl 13, X = Br 14, X = I 15; R = C₅H₁₀, X = Cl 16, X = Br 17; X = I 18; R₂ = Ph₂, X = Cl 19, X = Br 20, X = I 21; 57–81%). In contrast to the ZnII-mediated hydration of conventional nitriles, which proceeds only in the presence of co-catalyzing oximes or carboxamides, the reaction with cyanamides does not require any co-catalyst. Complexes 1–9, 12–19 were characterized by 1H, 13C{1H} NMR, IR, HRESI-MS, and X-ray crystallography (for 1–3, 8, 9, 13–15, and 17), whereas 20 and 21 were characterized by HRESI+-MS and 1H and 13C{1H} NMR (for 20). The structural features of the cyanamide complexes 1, 2, 7, and 8 were interpreted by theoretical calculations at the DFT level.