Vladimir MINKIN(h=36)

  1. V.I. Minkin, O.A. Osipov, Yu.A. Zhdanov. Dipole Moments in Organic Chemistry. Plenum Press: New York. 1970.
  2. V.I. Minkin, L.P. Olekhnovich, Yu.A. Zhdanov. Molecular Design of Tautomeric Compounds. Kluwer Publ. Dordrecht-Boston-Tokyo. 1988.
  3. V.I. Minkin, B.Ya. Simkin, R.M. Minyaev. Quantum Chemistry of Organic Compounds. Mechanisms of Reactions. Springer Verlag. Berlin. 1990.
  4. V.I. Minkin, M.N. Glukhovtsev, B.Ya. Simkin. Aromaticity and Antiaromaticity. Electronic and Structural Aspects. J.Wiley Intersci. New York. 1994.
  5. R. Hoffmann, V.I. Minkin, B.K. Carpenter. Ockham's Razor and Chemistry. Bull. Soc. Chim. France, 1996,133, 117-130; Hyle (Intern. J. Philosophy), 1997, 3, 3-28.
  6. V. I. Minkin, R.M. Minyaev Cyclic Aromatic Compounds with Hypervalent Centers. Chem. Rev., 2001, 101, 1247-1265. (IF=40.197)
  7. A.V. Metelitsa, V.V. Lokshin, J.-C. Micheau, A. Samat, R. Guglielmetti, V.I. Minkin. "Photochromism and Solvatochromism of Push-Pull or Pull-Push Spiroindolinonaphthoxazines". Phys. Chem. Chem. Phys. 2002, 4, 4340-4345. (IF= 3.573)

ABSTRACT: The photochromic and solvatochromic behaviour of 17 variously substituted spiroindoline naphthoxazines has been investigated in cyclohexane, toluene, acetonitrile and methanol in fluid solution. Specific parameters such as the wavelengths and the molar absorption coefficients of the closed spiro- and open merocyanine forms, together with the photocoloration and photobleaching quantum yields, rate constants and activation energies of thermal fading have been determined under continuous monochromatic irradiation. It has been shown that most of these parameters are closely related to the electron distribution on the highly conjugated photomerocyanines and on their quinoidal or zwitterionic character. Depending on the acceptor or donor properties and on the position of their substituents, three classes of compounds have been detected.

  1. R.M. Minyaev, V.I. Minkin, T.N. Gribanova, A.G. Starikov, R. Hoffmann. "Poly[n]prismanes. A Family of Stable Cage Structures with Half-Planar Carbon Centers". J. Org. Chem., 2003, 68 (22), 8588-8593. (IF= 4.450)

ABSTRACT: A series of bi[n]prismanes and tri[n]prismanes (n = 3−6) containing n and 2n, respectively, tetracoordinated carbon centers with nonclassical bisphenoidal (half-planar) configuration has been designed computationally.

  1. V.I. Minkin. Photo-, Thermo-, Solvato- and Electrochromic Spiroheterocyclic Compounds. Chem. Rev., 2004, 104, 2751. (IF=40.197)
  2. A.D. Dubonosov, V.A. Bren, V.I. Minkin. The Photochemical Reactivity of the Norbornadiene- Quadricyclane System. In: Organic Photochemistry and Photobiology (Eds.W. Horspool, F. Lenci). Ch. 17, 1-34.CRC Press. Boca Raton-London-New York. 2004.
  3. V.I. Minkin, R. M. Minyaev. Hypercoordinate Carbon in Polyhedral Organic Structures. Mendeleev Commun., 2004, 43-46. (IF=0.901)

ABSTRACT: Carbon holds a unique position among the elements. It forms more than 14 millions of currently known organic compounds, structural organization of which is governed by the beautifully simple principles of tetravalence and tetrahedral stereochemical configuration. In the past decades, the edifice of the classical structural theory of organic compounds has been complemented with new approaches allowing a rational design of polyhedral clusters with hypercoordinate carbon centres.

  1. V.I. Minkin, A.V. Metelitsa, I.V. Dorogan, B.S. Lukianov, S.O. Besugliuy, J.-C. Micheau. "Spectroscopic and Theoretical Evidence for the Elusive Intermediate of the Photoinitiated and Thermal Rearrangements of Photochromic Spiropyrans". J. Phys. Chem. A, 2005, 109, 9605-9616. (IF=2.946)

ABSTRACT: Spectral properties and photochromic behavior of a series of novel 1‘,3‘,3‘-trimethyl-1,2-tetramethylenespiro[7H-furo(3,2-f)-(2H-1)-benzopyran-7,2‘-indolines] 1−4 have been studied. The mechanism of the photoinitiated ring-opening reaction involves the formation of an acoplanar cis−cisoid intermediate, the lifetime of which in the case of 6-(tert-butyl) derivative 4 is long enough to observe its absorption and fluorescence spectra under conditions of continuous irradiation. The occurrence of the intermediate on the reaction paths of the thermal and photochemical ring-opening processes has been also shown by the DFT and CIS calculations. The TD-B3LYP/6-31G**//HF/6-31G** calculated spectrum of the intermediate well matches that observed experimentally. For spiropyran 3 with a 6-NO2 group, kinetic and activation parameters of the photoinitiated coloration and dark bleaching reactions have been determined.

  1. R.M. Minyaev, T.N. Gribanova, V.I. Minkin, A.G. Starikov, R. Hoffmann. Planar and Pyramidal Tetracoordinate Carbon in Organoboron Compounds. J. Org. Chem. 2005, 70, 6693-6704. (IF= 4.450)

ABSTRACT: Using previously proposed C(BH)2(CH)2 (16, 17) and C(CH)2B2 (22) systems with a central planar tetracoordinate carbon (ptC) atom linking two three-membered rings as building blocks, a series of stable structures containing two and three ptC centers within a molecule have been designed and computationally studied with the DFT (B3LYP/6-311+G**) method. Inclusion of a carbon atom ligated with π-accepting and σ-donating boron centers into at least one aromatic ring is critical for stabilization of a planar structure. A square pyramidal configuration at tetracoordinate carbon may be achieved in appropriately strained molecules such as [3.3.3.3]tetraborafenestrane 45 and others by surrounding the carbon with boron-centered ligands.

  1. I.D. Sadekov, G.A. Abakarov, V.I. Minkin. "Five-membered heterocycles with Vicinal Te and O Heteroatoms". Advances Heterocycl. Chem. 2006, 92, 55-82. (IF=1.818)
  2. V.I. Minkin. 'Photoswitchable Molecular Systems Based on Spiropyrans and Spirooxazines". In: Molecular Switches (B.L. Feringa and W.R. Browne eds.). Vol. 1. Ch.2. Pp. 37-80. Wiley-VCH. 2011.
  3. V.I. Minkin, A.V. Tsukanov, A.D. Dubonosov, V.A.Bren. "Tautomeric Schiff bases: Iono, solvate, thermo-and photochromism". J. Mol. Struct. 2011, 998, 179-191. (IF=1.634)

ABSTRACT: The review article summarizes the recent data about novel tautomeric iono-, solvato-, thermo- and photochromic Schiff bases. This contribution focuses on the factors determining tautomeric equilibrium and on the investigations into the proton transfer mechanisms.

  1. T.N. Gribanova, R.M. Minyaev, V.I. Minkin. "Induced aromaticity and electron-count rules for bipyramidal and sandwich complexes of s- and d-metals". Open Org. Chem. J. 2011, 5 (Suppl. 1-M4), 62-78.

ABSTRACT: Structures and stability of an extended series of bipyramidal, sandwich and sandwich-bipyramidal mixed complexes formed by conjugated cyclic hydrocarbons (CH)n with s- (Li, Na, K, Be, Mg, Ca) and d- (Cr, Mn, Fe) metals have been studied using DFT B3LYP/6-311+G(df,p) calculations. Stable structures of the compounds satisfy a general (6n + 6d + 12c) electron-count rule, where n stands for total number of the basal hydrocarbon rings, d is total number of d-metal centers (or separate sandwich moieties) and c is total number of apical metal-carbonyl groups. It is shown that stabilization of the studied polyhedral organometallic structures (induced aromaticity) is caused by filling 6π-electronic shells of basal (4-6)-membered cycles provided by donation of additional electrons from metal centers thereby acquiring closed 18-electron shells.

  1. A.A. Milov, R.M. Minyaev, V.I. Minkin. "Intramolecular Hypervalent Interaction in the Conjugate Five-Membered Rings". J. Phys. Chem. A, 2011, 115, 12973-12982 (IF=2.946)

ABSTRACT: The intramolecular hypervalent interaction between the electron abundant atomic centers X and Y belonging to the IV–VI groups and second and fourth periods has been computationally studied on a model quasi-cyclic conjugate five-membered ring system 9 using the CCSD/6-311+G** and DFT B3LYP/6-311+G** methods. Electronic and structural factors affecting the strength and geometrical characteristics of the hypervalent X←Y interaction were analyzed based on the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. The donor–acceptor nY→σ*XR interaction has been shown to be the central factor correlating all important properties of the studied hypervalently bonded compounds 9.

  1. V.I. Minkin, A.A. Starikova, R.M. Minyaev Computational design of valence tautomeric adducts of CoII diketonates with redox-active o-benzoquinone1 ligands // Dalton Trans., (2012), DOI:10.1039/c2dt31567j. (IF=3.838)

ABSTRACT: A new concept for the structural design of valence tautomeric (VT) metal complexes involving the formation of stable adducts of a tetracoordinate transition metal complex with a suitable bidentate redox-active ligand has been computationally studied using the DFT B3LYP*/6-311++G(d,p) method. The calculations, performed on a series of adducts of CoII diketonates with o-benzoquinone and its mono- and diimines, showed that the mixed-ligand complexes of bis-(hexafluoroacetylacetonate) CoII with o-benzoquinone, o-benzoquinone imine and o-benzoquinone diimine satisfy the whole set of necessary conditions to be met by compounds exhibiting VT behaviour (stability of the adduct with respect to dissociation into the components, energy preference of the low-spin electronic state and thermally achievable energy barrier to intramolecular electron transfer determining the intrinsic mechanism of VT rearrangements). These compounds can be regarded as a feasible synthetic target of a broad series of mixed-ligand VT complexes.

AleksandrPOZHARSKII(h=26)

1. Pozharskii, A.F. Naphthalene 'proton sponges' Russian Chemical Reviews, 1998, 67 (1), pp. 1-24 (IF=2.644)

ABSTRACT: Methods of synthesis, physicochemical and structural characteristics, and reactivity of 1,8-bis(dialkylamino)naphthalenes and some of their close analogues pertaining to the class of so-called 'proton sponges' are considered. The bibliography includes 154 references.

2. Sorokin, V.I., Ozeryanskii, V.A., Pozharskii, A.F. A simple and effective procedure for the N-permethylation of amino-substituted naphthalenes, European Journal of Organic Chemistry, 2003, (3), pp. 496-498 (IF=3.329)

ABSTRACT: A wide range of amino-substituted naphthalenes can be N-permethylated by the system Me2SO4/Na2CO3/H2O(alcohols) with good to excellent yields. Steric hindrance does not prevent the reaction. Some amines with electron-withdrawing groups, especially at nonconjugated positions, are also alkylated. The procedure allows the combination of a reduction (catalytic or by tin dichloride in acidic media) and a methylation in a one-pot process. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

3. Pozharskii, A.F. Naphthaldehydes, Russian Chemical Reviews, 2003, 72 (5), pp. 447-470 (IF=2.644)

ABSTRACT: Data on methods for the preparation of naphthaldehydes, their physicochemical properties, structural characteristics and reactivities are generalised. Particular attention is given to procedures for formylation of naphthalenes and peri-interactions involving the aldehyde group in the α-position. The bibliography includes 201 references.

4. Pozharskii, A.F., Ryabtsova, O.V., Ozeryanskii, V.A., Degtyarev, A.V., Kazheva, O.N., Alexandrov, G.G., Dyachenko, O.A. Organometallic Synthesis, Molecular Structure, and Coloration of 2,7-Disubstituted 1,8-Bis(dimethylamino)naphthalenes. How Significant Is the Influence of "Buttressing Effect" on Their Basicity?, Journal of Organic Chemistry, 2003, 68 (26), pp. 10109-10122 (IF=4.450)

ABSTRACT: On treatment of 2,7-dilithio- (6a) and 2,7-bis(bromomagnesio)- (6b) naphthalenes with a number of electrophiles, new “proton sponge” derivatives 7a−e,g, containing iodo, methylthio, trimethylsilyl, methyl, n-butyl, and ethoxycarbonyl groups in ortho-positions to dimethylamino groups, have been synthesized. The investigation of their molecular structure, spectral characteristics, and basicity reveals that the latter is mainly determined by two groups of factors: (1) the polar effect of ortho-substituents and (2) the so-called “buttressing effect” representing the complex combination of various sterical interactions of ortho-substituents with dimethylamino groups in corresponding bases and cations. A contradictory directionality of these interactions strongly reduces the importance of the buttressing effect in the case of compounds with bulky ortho-substituents, which is most clearly displayed in the absence of any relationship between the size of ortho-substituents and the basicity. On the contrary, for proton sponges having in ortho-positions the electron-donating groups with lesser steric demands, both the buttressing and the polar effects act in the same direction. This is the reason for the exceptionally high basicity of 2,7-dimethoxy- (2) and tetrakis(dimethylamino)- (3a) naphthalenes. It has been found that bis(trimethylsilyl)-bis(dimethylamino)naphthalene 7d has an in-out configuration of the NMe2 groups in the solid that is the first example of its kind in the series of naphthalene proton sponges. The origin of a yellow coloring of 2,7-disubstituted proton sponges is also discussed.

5. Sorokin, V.I., Ozeryanskii, V.A., Pozharskii, A.F. Exclusive β-substitution in the reaction of octafluoronaphthalene with secondary amines, European Journal of Organic Chemistry, 2004, (4), pp. 766-769 (IF=3.329)

ABSTRACT: The reaction between octafluoronaphthalene and dimethylamine, pyrrolidine or piperidine in DMF, dimethyl(ethylene)urea (DMEU) or without solvent leads to the exclusive substitution of β-fluorine atoms giving naphthalene derivatives with four NR2 groups. This was proved by 19F NMR of the products and a crystal structure determination for 1,4,5,8-tetrafluoro-2,3,6,7-tetrakis(piperidin-1-yl)naphthalene. The main feature of the reaction in DMF was a transamidation process. The remaining four fluorine atoms in the synthesised tetraamines could be smoothly replaced by reduction with LiAlH4. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

6. Szemik-Hojniak, A., Deperasińska, I., Buma, W.J., Balkowski, G., Pozharskii, A.F., Vistorobskii, N.V., Allonas, X. The asymmetric nature of charge transfer states of the cyano-substituted proton sponge, Chemical Physics Letters, 2005, 401 (1-3) , pp. 189-195 (IF=2.337)

ABSTRACT: The geometric and electronic structure of 1,8-bis(dimethylamino)-4-cyano-naphthalene (DMAN-CN) and its mono-protonated cation (H+DMAN-CN) have been investigated by density functional theory (DFT) and time dependent density functional theory (TD-DFT) methods. Ground state geometry optimization leads to a significant structural asymmetry and polarity of both molecules. Vertical excitation energies and oscillator strengths calculated for the lower-lying excited singlet states of DMAN-CN are in excellent agreement with experimental absorption maxima in n-hexane. Similarly, it is found that experimentally observed solvatochromic shifts are favourably reproduced by the calculations. The calculations reveal that the S1 and S2 states of the neutral molecule and the S3 state of the cation are characterised by an asymmetric charge transfer, i.e., the two dimethylamino groups contribute unequally to the transfer of charge to the cyanonaphthalene moiety.

7. Pozharskii, A.F., Gulevskaya, A.V. Pyrimido[4,5-c]pyridazine-5,7(6H,8H)-diones: Marvelous substrates for study of nucleophilic substitution of hydrogen, Journal of Heterocyclic Chemistry, 2005, 42 (3) , pp. 375-385 (IF=1.220)

ABSTRACT: The data on nucleophilic substitution reactions of hydrogen in 6,8-dimethylpyrimido[4,5-c]pyridazine- 5,7(6H,8H)-dione, its 3-chloride, N2-oxide and some other derivatives are reviewed. All these compounds possess a remarkable ability to undergo not only simple functionalizations but also tandem and cascade transformations leading to annelation of various heterocyclic rings.

8. Pozharskii, A.F., Ryabtsova, O.V., Ozeryanskii, V.A., Degtyarev, A.V., Starikova, Z.A., Sobczyk, L., Filarowski, A. 2-α-hydroxybenzhydryl- and 2,7-di(α-hydroxybenzhydryl)-1,8- bis(dimethylamino)naphthalenes: The first examples of stabilization of in/out proton sponge conformers by intramolecular hydrogen bonding. The most flattened amino group ever participating in IHB, Tetrahedron Letters, 2005, 46 (23) , pp. 3973-3976 (IF=2.683)

ABSTRACT: 2-(α-Hydroxybenzhydryl)- 6 and 2,7-di(α-hydroxybenzhydryl)-1,8-bis(dimethylamino)naphthalenes 8 have been shown to exist in crystals as in/out conformers stabilized by O–H⋯N intramolecular hydrogen bonding. In agreement with X-ray studies, the NMR data are also consistent with 7 retaining its in/out form in solution, whilst for 8 superimposed equilibrating in/out–out/in conformers are observed.

9. Serduke, O.V., Gulevskaya, A.V., Pozharskii, A.F., Starikova, Z.A., Profatilova, I.A. Cycloalkano[1″,2″:4,5;4″,3″:4′,5′] bis(pyrrolo[2,3-c]pyrimido[5,4-e]pyridazines): Synthesis, structure and mechanism of their formation, Tetrahedron, 2006, 62 (4) , pp. 652-661 (IF=3.025)

ABSTRACT: Reactions of 3-alkylamino-6,8-dimethylpyrimido[4,5-c]pyridazine-5,7(6H,8H)-diones with cyclohexyl- and cycloheptylamines in the presence of AgPy2MnO4 produce novel cycloalkano[1″,2″:4,5;4″,3″:4′,5′]bis(pyrrolo[2,3-c]pyrimido[5,4-e]pyridazines). Detailed information concerning the scope and mechanism of these transformations is discussed.

10. Pozharskii, A.F., Ryabtsova, O.V. Organolithium and organomagnesium compounds of the naphthalene series in organic synthesis, Russian Chemical Reviews, 2006, 75 (8) , pp. 709-736 (IF=2.644)

ABSTRACT: The review summarises procedures for the synthesis of organolithium and organomagnesium compounds of the naphthalene series, including binaphthyls, the properties of these compounds and their use in organic synthesis.

11. Gulevskaya, A.V., Pozharskii, A.F. Nucleophilic Aromatic Substitution of Hydrogen as a Tool for Heterocyclic Ring Annulation, Advances in Heterocyclic Chemistry, 2007, 93 , pp. 57-115 (IF=1.818)

ABSTRACT: SNH methodology finds significant use in organic synthesis. A major advantage of this methodology is that it eliminates the necessity of first introducing a good leaving group into an aromatic substrate. Moreover, in classical SNipso reactions an acid, such as HHal, H2SO4 or HNO2 is normally liberated that has to be scavenged. However, in SNH processes, a water molecule is typically formed that can contribute to “green chemistry.” This chapter deals with SNH cyclizations. SNH based heterocyclizations allow the synthesis of a great variety of heterocyclic structures differing in ring size, number of heteroatoms and their type, and degree of unsaturation. Various arenes and hetarenes with appropriate electron deficiency can be used as substrates. In context to future prospects, it is observed that a large number of known SNH cyclizations deals with the pyrrole ring closure, therefore search for new substrates, reagents, and cyclization schemes for the annulation of other heterocyclic rings is desirable. It is also important to optimize reaction conditions as many existing transformations do not provide high enough yields.

12. Pozharskii, A.F., Degtyarev, A.V., Ryabtsova, O.V., Ozeryanskii, V.A., Kletskii, M.E., Starikova, Z.A., Sobczyk, L., Filarowski, A. 2-α-hydroxyalkyl- and 2,7-di(α-hydroxyalkyl)-1,8- bis(dimethylamino)naphthalenes: Stabilization of nonconventional in/out conformers of "proton sponges" via n⋯H-O intramolecular hydrogen bonding. A remarkable kind of tandem nitrogen inversion, Journal of Organic Chemistry, 2007, 72 (8) , pp. 3006-3019 (IF=4.450)

ABSTRACT: A regular set of 2-(α-hydroxymethyl)- and 2,7-di(α-hydroxymethyl)-1,8-bis(dimethylamino)naphthalenes has been prepared. Their X-ray, NMR, and IR studies have demonstrated that in tertiary mono-alcohols the orientation of free nitrogen electron pairs in crystals and solution corresponds to nonconventional in/out conformers stabilized by O−H···N intramolecular hydrogen bonding. For tertiary 2,7-dialcohols, the superimposed equilibrating in/out−out/in nitrogen invertomers are observed in solution. Unlike this, primary and secondary mono- and dialcohols commonly exist in the in/in form, which is typical for the parent proton sponge and the majority of its derivatives.

13. Serdyuk, O.V., Gulevskaya, A.V., Pozharskii, A.F., Avakyan, V.E. Benzobis(pyrrolopyrimidopiridazines): Molecular structure and properties of the first π-electronic analogues of dibenzo[a,o]picene, Journal of Heterocyclic Chemistry, 2008, 45 (1) , pp. 195-199 (IF=1.220)

ABSTRACT: Molecular structure, aromaticity and some spectral properties of benzobis(pyrrolopyrimidopiridazines) 2 that are the first -electronic analogues of the still unknown dibenzo[a,o]picene are discussed.

14. Gulevskaya, A.V., Burov, O.N., Pozharskii, A.F., Kletskii, M.E., Korbukova, I.N. Oxidative alkylamination of azinones as a direct route to aminoazinones: study of some condensed diazinones, Tetrahedron, 2008, 64 (4) , pp. 696-707 (IF=3.025)

ABSTRACT: Oxidative alkylamination of azinones is a promising method for the preparation of a great variety of alkylaminoazinones. Treatment of 6,8-dimethyl-2-R-pyrimido[4,5-c]pyridazin-3,5,7(2H,6H,8H)-triones 7, 1,3-dimethyl-5-R-pteridin-2,4,6(1H,3H,6H)-triones 8 and 1,3,6-trimethylpyrimido[4,5-d]pyrimidin-2,4,7(1H,3H,6H)-trione 9 with alkylamine/AgPy2MnO4 or alkylamine/KMnO4 has been shown to produce their 4-, 7- and 5-alkylamino derivatives, respectively, in good yields. While 1-methylquinoxalin-2(1H)-one 10 is smoothly alkylaminated under the above conditions giving 3-alkylamino derivatives, quinoxaline itself does not take part in this reaction. Factors influencing oxidative alkylamination of azinones and a regioselectivity of the process are discussed.

15. Degtyarev, A.V., Ryabtsova, O.V., Pozharskii, A.F., Ozeryanskii, V.A., Starikova, Z.A., Sobczyk, L., Filarowski, A. 2,7-Disubstituted proton sponges as borderline systems for investigating barrier-free intramolecular hydrogen bonds. Protonated 2,7-bis(trimethylsilyl)- and 2,7-di(hydroxymethyl)-1,8-bis(dimethylamino)naphthalenes, Tetrahedron, 2008, 64 (27) , pp. 6209-6214 (IF=3.025)