Charge-transfer complexes of indenophanes with π-acceptors

The charge-transfer (CT) spectra of the -complexes formed by a number of -acceptors with several indenophanes as well as indene as a model compound have been measured in methylene chloride at 20 °C. Association constants and transition energies of these complexes as well as ionization potentials of the -donors have been determined. The data obtained indicate the existence of transannular electronic interactions in the indenophane nucleus. Furthermore, the pseudo-para- andmeta[2.2]indenophane isomers (3 and4) show a large difference in their -base strength. A good linear relationship has been observed between the association constants and _max of the long wavelength CT bands for the -complexes of these -donors with both tetracyanoethylene (TCNE) and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). All CT complexes studied have a 1:1 stoichiometry.

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Charge-transfer-Komplexe aus Indenophanen und -Akzeptoren

Zusammenfassung Die Charge-transfer-Spektren (CT-Spektren) von -Komplexen aus Indenophanen bzw. der Modellverbindung Inden und verschiedenen -Akzeptoren wurden in Methylenchlorid bei 20 °C bestimmt. Die Assoziationskonstanten und Übergangsenergien dieser Komplexe sowie die Ionisationspotentiale der -Donatoren wurden ermittelt. Die Daten sprechen für das Vorliegen transannularer elektronischer Wechselwirkungen im Indenophan-System. Die isomeren pseudo-para- und -meta[2.2]indenophane3 und4 unterscheiden sich in ihrer -Basizität deutlich. Es besteht eine gute lineare Korrelation zwischen den Assoziationskonstanten und _max der langwelligen CT-Banden der verschiedenen -Donatoren mit Tetracyanoethylen (TCNE) und 2,3-Dichlor-5,6-dicyano-p-benzochinon (DDQ). Alle untersuchten CT-Komplexe besitzen 1:1-Stöchiometrie.

     

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.     

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.     

Ab initio SCF and CI study of the electronic spectrum of pyridine N-oxide

Configuration interaction (CI) studies of ground, n *, * * electronically excited states are reported for pyridine N-oxide. The transition energy to the lowest * excited ¹ B ₂ state is calculated at 4.35 eV, compared to the experimental spectrum range of 3.67–4.0 eV. This state lies below the lowest n * excited ¹ A ₂ state calculated at 4.81 eV above the ground state. The only experimentally reported triplet state at 2.92 eV above the ground state is predicted to be the ³ A ₁ (*) state. The calculated energy lies at 3.27 eV. Numerous other high-lying singlet states as well as the triplet states have also been calculated. The intramolecular charge transfer character of the ground and the excited states have been studied in terms of the calculated dipole moment and other physical properties.     

A thermodynamic and structural study of the interactions of pyridino- and diketopyridino-18-crown-6 ligands with some primary organic ammonium cations

Equilibrium constant (K), enthalpy change (H), and entropy change (S) values have been determined calorimetrically at 25°C in 90%MeOH 10%H₂O (v/v) for the interactions of pyridino-18-crown-6 (P18C6) and diketopyridino-18-crown-6 (K₂P18C6) with perchlorate salts of ammonium, benzylammonium,-phenylethylammonium,-phenylethylammonium, and-(1-naphthyl)ethyl-ammonium cations. The crystal structure of the complex of P18C6 with benzylammonium perchlorate was determined by X-ray crystallography. The¹H 1D and 2D NMR spectra of some of these complexes were used to elucidate their structural features in solution. The logK values for the interaction of the ammonium cations with P18C6 are larger than those with K₂P18C6, probably due to the higher degree of structural flexibility of P18C6. Ligand K₂P18C6 displays appreciable - interaction with the-(1-naphthyl)ethylammonium cation, but not with the-phenylethylammonium cation.- interaction between ligand and cationSupplementary Data relating to this article are deposited with the British Library as Supplementary Publication No SUP 00000 (22 pages)     

On the excited states ofp-quinones and an interpretation of the photocycloaddition ofp-quinones to alkenes

A theoretical investigation is made of the electronic states ofp-benzoquinone (PBQ), methyl substituted PBQ's and 1,4-naphthoquinone (NQ). In accord with experiment, the lowest triplet state of PBQ is calculated to be³ B _1g (n, *), while that for duroquinone (DQ) is³ B _3g (, *). The electron densities of these states are consistent with the hypothesis that³ n, * states lead to oxetan formation and³, * states to cyclobutanes. It is predicted that trimethyl PBQ might form both adducts, as the two states are calculated to be nearly degenerate.The photochemistry of NQ is more complex. The lowest excited triplet state is calculated to be ofn, * symmetry, in accord with experiment; however, several other states are predicted near in energy, and the photochemistry cannot be rationalized unambiguously.This work was supported in part by the National Research Council of Canada.     

Charge control in the formation of complexes of phenol with unsaturated compounds containing organometallic substituents from group IV

The resonance donor effect of the , conjugation of R₃M and R₃MCH₂ (M = Si, Ge, Sn; R is an alklyl group) substituents with the triple bond in compounds R₃MC=CX and R₃MCH₂CCX (X = H, R) changes on passing from isolated molecules to their H-complexes. A partial ⁺ charge on the triple bond enhances , conjugation; a partial ^– charge on the triple bond has practically no effect on the resonance properties of R₃M substituents, whereas the , conjugation of R₃MCH₂ substituents diminishes owing to the effect of negative direct resonance interaction. The effect of , conjugation on the effective negative charges of the carbon atoms in the -CC- fragments was estimated quantitatively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1041–1046, June, 1994.This work was supported by the Russian Fundation for Basic Research (Grant 93-03-18372).     

Triplet states via intermediate neglect of differential overlap: Benzene,pyridine and the diazines

The intermediate neglect of differential overlap technique is modified and applied to the calculation of excited triplet states. The resulting method generally reproduces the transition energies of the better-classified observations within a rms error of 1000 cm^–1. Trends are well reproduced, and the calculated orders ofn-* and -* triplet states are in good accord with the experimental information to date.The method is applied to benzene and the azines. The lowest four triplet states of benzene are calculated in good accord with experiment. Pyridine is calculated to have an-* triplet nearly degenerate with the lowest lying -* triplet, corroborating suggestions of Japar and Ramsay based on experimental information. A detailed analysis is made of the diazines, and assignments are suggested for the higher lying triplet states not yet classified or not yet observed.     

An ab initio study of formamide

Calculated energy and molecular properties of the ground and low-energy excited states of formamide are presented at the ground state geometry. Satisfactory results are obtained except for the ¹* energy which remains too high by 1 eV (which is nevertheless a large improvement over previous calculations). The predicted triplet energies lie at 5.4 eV (³ n*) and 5.8 eV (³*).     

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.     

Ab initio studies of the low-lying π-states of borazine

Self-consistent-field and configuration-interaction studies were performed on borazine, using a double-zeta basis set augmented by six diffuse -functions. Low-lying singlet and triplet states of the A ₁ , A ₂ and E species were calculated, corresponding to ^* excited valence and Rydberg states. A selection out of singly and doubly excited configurations relative to a set of reference configurations was made for each species. Calculated vertical excitation energies (in eV) are 7.12 for ¹ A ₂(V), 8.45 for ¹ E (3p-R), 8.57 for ¹ A ₁(V), 8.9 for ¹ E(V-R), 9.55 for ¹ E(3d-R), 6.98 for ³ A ₁(_V), 7.27 for ³ E(V), 7.82 for ³ A ₂(V), 8.30 for ³ E(3p-R), and 9.5 for ³ E(3d-R), where V and R refer to valence or Rydberg character. The results are compared with experimental excitation energies, previous ab initio studies of borazine, and with recent ab initio studies of benzene.Dedicated to Professor Dr. H. Hartmann on the occasion of his 65th birthday.     

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.

     

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.     

Molecular orbital calculations on the optical rotatory properties of chiral allene systems

The chiroptical properties associated with the ^* transitions in dissymmetric allene systems are calculated and relationships between the chiroptical observables and the stereochemical and electronic structural features of these systems are examined. The calculations are based on the INDO and CNDO/S semiempirical molecular orbital models for the electronic structure of the molecular systems and excited states are constructed in the virtual orbital-configuration interaction approximation. The dipole strengths, rotatory strengths, and dissymmetry factors for the three lowest energy ^* transitions are computed and reported for eleven chiral allene structures. Relationships between absolute configuration and the signs of the ^* rotatory strengths are examined and discussed.     

Excited states of phenyl carbonyl compounds

In an attempt to clarify the origin of the dual phosphorescence in phenyl alkyl ketones, we have made some calculation (within the C.I.P.S.I. method in an excitonic scheme) to elucidate the conformation of both ground states and excited states of propiophenone. Our calculations have shown the presence of two stable isomers in the ground state, first n ^* state, and first ^* singlet and triplet states. So our work suggests that the origin of the dual phosphorescence of propiophenone could be related to the conformational change of the molecule in the n ^* state, because the most stable conformations in the n ^* state and in the ground state are different.     

Theoretical Study of the Products of Acetylene Addition to HgCl2

The ab initio MP2 method is used with the LANL2DZ basis to calculate the mercury chloride ,-complex with two acetylene molecules (1) and various isomeric forms of mercury di()-vinyl chloride -complexes (2): cis-cis (2A), cis-trans (2B), and trans-trans (2C). The ,-complex is the most stable form of all those considered; the difference between 1 and 2A is 24.9 kcal/mole. A relation between the total energies (kcal/mole) for isomeric forms 2 is established to be 2A (0) < 2B (0.98) < 2C (1.58). Complex 1 is shown to be transformed into 2A via the intermediate formation of 3, which is a hybrid form of the complex (,-complex of mercury chloride with two acetylene molecules). The structures of the transition states for the transformations of 1 into 3 (structure 4) and of 3 into 2A (structure 5) and the corresponding transition activation energies are determined. The interaction of 2A, 2B, and 2C with the Cl^- anion as a model nucleophile is considered. It is shown that the resulting anions (6A, 6B, 6C) have a planar structure with the relative stability increasing in the series 6A<6B<6C.     

Calculations on the π→1π* transitions in large conjugated carbonyl compounds using the molecules-in-molecules method

Assignments of the ^1* electronic transitions in large carbonyl compounds have been carried out using the molecules-in-molecules method.     

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.     

Solvatochromic parameters for binary mixtures and a correlation with equilibrium constants. Part I. Dioxane-water mixtures

The values of the solvatochromic parameters and were determined at 25°C for dioxane-water mixtures from 0 to 100% of dioxane. These values as well as those of the Reichardt polarity parameter E _T (30) and the polarity-polarizability ^* are correlated with acid dissociation constants and other equilibrium constants in solvent mixtures of the same composition. As a general rule, two linear zones with different slopes are obtained, one zone covering water-rich solutions, and the other dioxane-rich solutions. The change in behavior takes place at about 55% (v/v) dioxane for all equilibria studied. A fit of pK to an equation of the multiparametric form proposed by Kamlet and Taft shows in most cases a linear dependence on ^* alone, in other cases a dependence on ^* and .     

Additive nodal increments for approximate calculation of the total π-electron energy of benzenoid hydrocarbons

An approximate method that allows efficient calculation of the total -electron energy (E ) of benzenoid hydrocarbons is presented. It is based on an additive scheme taking into account the characteristic features of variously annelated benzene rings expressed in terms of the numbers corresponding to the different nodes of the dual graph of the hydrocarbon molecule. The parameters of the model are fitted by a test calculation on 1030 hydrocarbons. The mean square error obtained in E is 0.07%. The method provides a connection between the names of hydrocarbons and their stabilities.