On the Distribution of π-Electrons into Rings of Conjugated Hydrocarbons Containing a Linear Polyacene Fragment

Summary. A method for assessing the -electron contents (EC) of rings of benzenoid hydrocarbons, based on the examination of their Kekulé structures, was recently put forward by Balaban and Randi. We now show that all hexagons belonging to a linear polyacene fragment of a conjugated hydrocarbon (not necessarily benzenoid) have mutually equal EC-values.     

Chemical interactions between 2-mercaptobenzazoles and π-acceptors

Summary 2-Mercaptobenzazoles (1a–c) interact with several -acceptors such as tetracyanoethylene (TCNE) 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL) dicyanomethyleneindane-1,3-dione (CNIND), 2,3-dicyano-1,4-naphthoquinone (DCNQ), 9-dicyanomethylene-2,4,7-trinitrofluorene (DTF), and 2,3-dichloro-1,4-naphthoquinone (DCHNQ)via the formation of charge-transfer (CT) complexes to yield various heterocyclic compounds.

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Chemische Wechselwirkungen zwischen 2-Mercaptobenzazolen und -Akzeptoren

Zusammenfassung Die 2-Mercaptobenzazole1a–c reagieren mit verschiedenen -Akzeptoren wie Tetracyanoethylen (TCNE), 2,3-Dichlor-5,6-dicyano-1,4-benzochinon (DDQ), 2,3,5,6-Tetrachlor-1,4-benzochinon (CHL), Dicyanomethylenindan-1,3-dion (CNIND), 2,3-Dicyano-1,4-naphthochinon (DCNQ), 9-Dicyanomethylen-2,4,7-trinitrofluoren (DTF) und 2,3-Dichlor-1,4-naphthochinon (DCHNQ) unter Ausbildung von charge transfer — Komplexen (CT) zu heterocyclischen Verbindungen.

     

Charge control of phenol complexation with unsaturated compounds containing organosilicon substituents. Thiophene derivatives

The frequency shifts of the O-H stretching modes and the resonance components _R of these shifts in the IR spectra of H-complexes of phenol with thiophene derivatives having organic and organosilicon substituents have been analyzed. Relationship of and _R parameters to values calculated by nonempirical methods that characterize the electronic effect of organic substituents on the effective charges of the thiophene ring atoms has been established. It has been shown that in the complexation of phenol (hard acid) with thiophene derivatives charge control prevails over frontier orbital control. The changes in the effective charges of the thiophene ring atoms due to the effect of organosilicon substituents have been calculated.For the previous publication of this series see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2163–2168, December, 1994.This work was supported by the Russian Foundation for Basic Research, Project No. 93-03-18725.     

Physicochemical properties of π-π complexes of zinctetraphenylporphyrin with aromatic molecules

Features of the solvation of zinctetraphenylporphyrin (ZnTPP) in benzene, toluene,ortho-, meta-, andpara-xylenes were studied by a thermogravimetric method. The temperature ranges of the stability and the compositions of the corresponding specific - complexes were determined from the results of the thermogravimetric investigation of the crystallosolvates of the metalloporphyrin with the solvent molecules, and the energy characteristics of the intermolecular metalloporphyrin—solvent interactions were calculated.Institute of the Chemistry of Nonaqueous Solutions, Russian Academy of Sciences, 153018 Ivanovo. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1545–1548, July, 1992.     

Quantum-chemical study of manifestations of conjugation in molecules containing conjugated C=C and C=O bonds

Based on the MNDO calculations of the electronic structure of the molecules of acrolein, glyoxal, and butadiene, possible mechanisms of the conjugation in systems containing conjugated C=C and C=O bonds have been analyzed. In the electronic ground state ofs-trans-acrolein, the , -conjugation is very small, whereas in the first excited electronic state, the conjugation is substantial, In the ground state ofs-trans-glyoxal, the ,-conjugation should manifest itself clearly but should be weaker than in butadiene, whereas in the first excited electronic state, this conjugation should be more pronounced, Alternation of double and single bonds in the classic structural formula of a molecule does not ensure that this molecule exhibits the properties of a -conjugated system even in planar conformations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1648–1652, July, 1996.     

Complexation of monosubstituted benzenes and methanes by cyclotetrachromotropylene in aqueous solution: Substituent effects on π-π and Ch-π interactions

The stability constantsK of 11 complexes formed in aqueous solution between several monosubstituted benzenes (C₆H₅X) and methanes (CH₃X) as guests and cyclotetrachromotropylene as host were determined by proton NMR spectroscopy. Variations ofK with the substituent X are attributed to the electronic effect of X and the presence of C–H or aromatic bonds, if any, interacting with the host bonds.     

Quantum-chemical study of allylic and vinylic compounds of fifth-group elements

Energies and oscillator strengths of the long-wave electronic transitions for several conformers of allyl- and vinylamine and allyl- and vinylphosphine have been calculated by the semiempirical quantum-chemical MNDO method. The electronic structure of these molecules is discussed in detail, and the spectral and conformational effects ofn, and , conjugation are analyzed. Some suggestions concerning possible conjugation effects in the allylic compounds of As, Sb, and Bi are made.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1551–1554, September, 1993.     

Calculation of some electronic excited states of formaldehyde

The optimized MO's of several excited states of formaldehyde have been calculated by means of a large basis set of modified Gaussian functions; particular attention has been paid to the * transition. The total energy of the various states has been obtained as the sum of the SCF and correlation energies; the last one has been calculated as a functional of the electronic density. The calculated values for the transition energies are in good agreement with the experiment. A strong interaction of the * state with the continuum is evidentiated; this fact can justify the absence of the * band in the absorption spectrum.     

Complexation of Paraquat Dication with Disodium 1,8-Disulfonato-3,4,5,6-Acridinetetracarboxylic Acid in Water

Disodium 1,8-disulfonato-3,4,5,6-acridinetetracarboxylic acidforms a complex of 1 : 1 stoichiometry with paraquatdication in water. The stability constant of thecomplex is 1.2 × 10⁴ M^-1 at 25 °C.     

Reactivity of pyrrole pigments,XXI: Structure and reactivity of Cu(II) and Zn(II) bilindione chelates

Summary Several Mn, Cu, and Zn chelates of etiobiliverdin-IV-, mesobiliverdin-IX, and its dimethyl ester are studied. The results show that the chemical constitution of the Cu biliverdin chelate corresponds to a formal metal oxidation state of (II) coordinated to a neutral radical of the NH trideprotonated biliverdin. The reactivity of the Cu(II) bilindione chelates in nucleophilic solvents agrees with that expected for a neutral radical structure of the ligand; in CH₃OH, they undergo oxidation towards dimethoxybilipurpurins. The magnetic behaviour of Cu(II) etiobiliverdinate-IV- in the solid state shows an intramolecular weak antiferromagnetic coupling d⁹Cu-to--radical (J=–23 cm^–1) and an intermolecular weak antiferromagnetic coupling -radical-to--radical (J=–45 cm^–1). The analogy of this magnetic behaviour to that of the cation radical of metalloporphyrins is discussed.

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Reaktivität von Pyrrolpigmenten, 21. Mitt.: Struktur und Reaktivität von Cu(II)- und Zn(II)-Chelaten von Bilindionen

Zusammenfassung Einige Mn, Cu and Zn Chelate von Etiobiliverdin-IV-, Mesobiliverdin-IX und seinem Dimethylester werden untersucht. Im Komplex koordiniert ein Metallatom (mit der Formalladung II) mit einem Neutralradikal des dreifach NH-deprotonierten Bilindions. Die Reaktivität des Komplexes gegenüber nukleophilen Lösungmitteln entspricht erwartungsgemäß dem eines neutralen -Radikals; in CH₃OH wird er zu Dimethoxybilipurpurin oxidiert. Bei Cu(II)-Etiobiliverdinat-IV beobachtet man im festen Zustand neben schwacher, antiferromagnetischer Kupplung zwischen d⁹Cu und -Radikal (J=–23 cm^–1) auch eine schwache, intermolekulare, antiferromagnetische Wechselwirkung zwischen zwei -Radikalen (J=–45 cm^–1). Dieses magnetische Verhalten wird dem des -Kationradikals von Metalloporphyrinen gegenübergestellt.

     

Inclusion of dynamic σ-π polarization in π-electronab initio calculations

Summary A method is presented, whereby dynamic - polarization, i.e. the correlation effect expressed by simultaneous (-*, -*) excitations, can be approximately included in a multi-reference configuration interaction (MRCI) or multi-configurational self-consistent field (MC-SCF) calculation, without need to explicitly correlate the sigma orbitals. The method, which we call the capacitance matrix method, is based on the use of conventional one-electron integrals, from which a polarization potential (SPP) contribution is computed and added to the one- and two-electron Hamiltonian. In the present form, the method requires one parameter for each type of atom, and one for each type of bond. These parameters were adjusted to reproduce the dynamic - polarization energy, computed by restricted multi-reference CI calculations, of a number of states of different hydrocarbons, and the agreement was within a few percent. Using the same parameters in CAS (Complete Active Space) SCF calculations of various states of benzene gives excitation energies, when SPP is included, which is comparable to those obtained by much more elaborate MRCI calculations.     

A structural analysis of the complexes of (S,S)-dimethylpyridino-18-crown-6 with (R) and (S)-[α-(1-naphthyl)ethyl]ammonium perchlorate by NMR techniques and molecular modeling

Significant - interaction is found in the complexes of (S, S)-dimethylpyridino-18-crown-6 with (R)- and (S)-[-(1-naphthyl)ethyl]ammonium perchlorate. This finding is supported by the¹H NOESY NMR spectral technique, greater chemical shift changes of aromatic protons in both host and guest molecules upon complexation, and by molecular mechanics calculations. Because of the flexibility of the ligand, the tripod hydrogen bonding causes¹³C relaxation times of all periphery carbons to decrease without significant selectivity. Rotational energy barrier calculations of the methyl groups of the complexed ligand also show that the (S, S)-host-(R)-guest is the more stable complex.     

Electrochemical synthesis of π-indenyl-π-(3)-1,2-dicarbollyliron(III)

Co-electrolysis of potassium 1,2-dicarbadodecahydroundecaborate and indene in 0.1N sodium bromide solution in dimethylsulfoxide using iron electrodes afforded -indenyl--(3)-1,2-dicarbollyliron(III).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 764–765, April, 1993.     

1,4-dioxins from methyl phenylchloropyruvate. Competition of the Darzens, Favorskii, and Gabriel reactions

The reaction of methyl phenylchloropyruvate with potassium phthalimide and sodium imidazolide leads to isomeric 2,5-dimethoxycarbonyl-3,6-diphenyl- and 2,6-dimethoxycarbonyl-3,5-diphenyl-1,4-dioxins.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1042–1056, August, 2000.     

Some peculiarities of π—π interactions between tetraphenylporphine metal complexes and aromatic solvents

The — complexes of metal tetraphenylporphinates with benzene, toluene, and xylenes were characterized by means of thermogravimetry. The ability of metalloporphyrins to form — complexes with certain -donor molecules depends largely on the -acceptor capacity of the macroheterocycle, and on the peculiarities of the metal—porphyrin coordinative linkage. Stoichiometry, energy parameters, and thermal stability of the - complexes of metalloporphyrins with various aromatic ligands are determined to a great extent by the molecular structure of solvents.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp.850–853, May, 1993.     

Quantum-chemical study of allylic compounds with two bonded heavy atoms

It has been shown by the CNDO method that the bathochromic shift of the long-wave absorption band in the transition from allylstannane to compounds of the type C=C-C-Sn-X and C=C-Sn-X (where X is a heavy atom) is connected with the formation of a low-energy vacant *_S-X orbital, localized mainly in the region of the Sn-X chemical bond, and of an occupied _Sn-X orbital, the energy of which is somewhat higher than of the _C-Sn orbital. The dependence of the position of the long-wave absorbance region on conformation is related to the fact that, in planar and nonplanar conformers, the long-wave transitions are of a different type ( * and *, respectively); the bathochromic shift is determined to a large degree by the difference in the energies of the highest occupied MO ( - ) in the s-trans form. In the nonplanar conformers the heavy atom orbitals interact with the -orbital of the ethylene moiety through the bridge group; this leads to a significant delocalization of the HOMO and to a considerable change in its energy. On the other hand, their interaction with the *-orbital in compounds of the C=C-C-Sn-X type is very low and does not favor the delocalization of lower vacant MO. In vinyldistannane the *-orbital is noticeably delocalized, due to the interaction with the *_Sn-Sn orbital in planar and with the *_Sn-Sn orbital in nonplanar conformers.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 636–641, March, 1992.     

Fullerene C60 as a η5- and η6-ligand in sandwich-type π-complexes with transition metals

The molecular and electronic structures of some hypothetical sandwich-type -complexes of transition metals with fullerene C₆₀ were modeled. The M-C₆₀ bonds in ⁵-C₆₀MCp⁺ complexes (M = Fe, Ru, Os) are less strong than the M-Cp bonds in ferrocene, ruthenocene, and osmocene, respectively. The ⁶-C₆₀MC₆H₆ complexes (M = Cr, Mo, W) should be less stable than their classical analogs (C₆H₆)M(C₆H₆). The coordination of a metal atom with the fullerene at its pentagonal face is more energetically favorable than at a hexagonal face.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 598–601, April, 1994.We are grateful to V. I. Sokolov for discussion of the results obtained. This study was supported by the Russian Foundation for Basic Research (grants 93-03-4101 and 93-03-18725).     

Vibrational spectra and structure of “staircase” carbonyl π-complexes of transition metals

FTIR spectra have been studied for staircase cyclopentadienyl complexes containing two or three metal carbonyl fragments bound by the metal-carbon bond Cp(CO)₂Fe-CpmMn(CO)₃ (1), Cp(CO)₂Fe-CpmFe(CO)₂CH₂Ph (2), Cp(CO)₂Fe-Cpm(CO)₂Fe-CpmMn(CO)₃ (3), Cp(CO)₂Mo-Cpm(CO)₂Fe-CpmMn(CO)₃ (4), Cp(CO)₃W-Cpm(CO)₂Fe-CpmMn(CO)₃ (5), Cp(CO)₂Fe-Cpm(CO)₂Fe-BmCr(CO)₃ (6), Cr(CO)₃Bm-CpmFe(CO)₂CH₂Ph (7), where Cp = ₅-C₅H₅, Cpm = ¹⁵-C₅H₄, Bm = ¹⁶-C₆H₅. Temperature-dependent FTIR spectra were measured inn-pentane solutions over a wide temperature range and in the low-temperature solid matrices of argon and nitrogen. Rotamers, formed due to rotation about the metal-carbon -bond, were found in solutions and matrices. A molecular mechanics calculation of1 proved the possibility of such rotation.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1952–1956, November, 1994.The authors are grateful to the Russian Foundation for Basic Research (project code No 93-03-18592) and to the International Science Foundation (project code No MEQ000).     

Konformationen diastereoisomererBis-(alkylaryl)-ether

Summary X-ray-analysis of the meso-ether2 showed the existence of two bridged species in the unit cell besides the expected molecule. The additional bonds between the 9- and 10-positions of the anthracene moieties were extraordinarily long. This fact leads to conclusions on the reactive behaviour of alkylaryl carbinoles upon acid-catalysed etherification.