3J(PCNH) in phosphorus substituted thioformamides as a configurational probe

Coupling between P and (N)? H has been observed in the ¹H{¹⁴N}NMR spectra of a series of phosphorus substituted thioformamides, R¹₂/P(X)C(S)NHR². For R² = H one of the two couplings constants ³J(PCNH) is much larger than the other. The larger constant is assumed to be ³J(PCNH) (trans) and the magnitude of ³J(PCNH) for several compounds with R² = Me or Ph is used to assign the configuration about the C(S)? N bond.     

Dicyanoketene and its isomers

Ab initio STO-3G calculations have been performed on dicyanoketene and its isomeric forms. Optimized nuclear configurations and relative stabilities are examined and compared with those of ketene and oxirene. Heats of formation and bond substitution energies are estimated.     

Nitrated isomers of 2‐(trichloromethyl)quinoline

In the closely related quinoline compounds 8‐nitro‐2‐(trichloromethyl)quinoline, (I), 6‐nitro‐2‐(trichloromethyl)quinoline, (II), and 5‐nitro‐2‐(trichloromethyl)quinoline, (III), all C₁₀H₅Cl₃N₂O₂, which are of both reactivity and pharmacological interest, and for which the biological activity and cytotoxicity appear to be based on the positions of the CCl₃ and nitro substituents, the nitro group is only coplanar with its aromatic substrate in (II). The deviation of the nitro group from coplanarity is concluded to be a function of both its position with respect to the trichloromethyl group and the intermolecular contacts in which it participates. The discrepancies between the crystal structures and the molecular shapes predicted by ab initio calculations are also explained in these terms. The quinoline ring is not rigorously planar in any of the structures, which may be explained by stress produced by the CCl₃ substituent.     

Thermodynamic properties of 5(nitrophenyl) furan-2-carbaldehyde isomers

Background

The aim of the current work was to determine thermo dynamical properties of 5(2-nitro phenyl)-furan-2-carbaldehyde, 5(3-nitro phenyl)-furan-2-carbaldehyde and 5(4-nitro phenyl)-furan-2-carbaldehyde.

Results

The temperature dependence of saturated vapor pressure of 5(2-nitro phenyl)-furan-2-carbaldehyde, 5(3-nitro phenyl)-furan-2-carbaldehyde and 5(4-nitro phenyl)-furan-2-carbaldehyde was determined by Knudsen’s effusion method. The results are presented by the Clapeyron–Clausius equation in linear form, and via this form, the standard enthalpies, entropies and Gibbs energies of sublimation and evaporation of compounds were calculated at 298.15 K. The standard molar formation enthalpies of compounds in crystalline state at 298.15 K were determined indirectly by the corresponding standard molar combustion enthalpy, obtained using bomb calorimetry combustion.

Conclusions

Determination of the thermodynamic properties for these compounds may contribute to solving practical problems pertaining optimization processes of their synthesis, purification and application and it will also provide a more thorough insight regarding the theoretical knowledge of their nature.

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Graphical abstract: Generalized structural formula of investigated compounds and their formation enthalpy determination scheme in the gaseous state

     

The structures and stabilities of cyanoguanidine (a dimer of cyanamide) and its isomers

Extensively optimized STO-3G calculations on dicyandiamide and three isomeric structures confirm the nuclear configuration of cyanoguanidine.     

Two isomers of Pd2(S2NC7H4)4

The dichloromethane solvates of the isomers tetrakis(μ‐1,3‐benzothiazole‐2‐thiolato)‐κ⁴N:S;κ⁴S:N‐dipalladium(II)(Pd—Pd), (I), and tetrakis(μ‐1,3‐benzothiazole‐2‐thiolato)‐κ⁶N:S;κ²S:N‐dipalladium(II)(Pd—Pd), (II), both [Pd₂(C₇H₄NS₂)₄]·CH₂Cl₂, have been synthesized in the presence of (o‐isopropylphenyl)diphenylphosphane and (o‐methylphenyl)diphenylphosphane. Both isomers form a lantern‐type structure, where isomer (I) displays a regular and symmetric coordination and isomer (II) an asymmetric and distorted structure. In (I), sitting on an centre of inversion, two 1,3‐benzothiazole‐2‐thiolate units are bonded by a Pd—N bond to one Pd atom and by a Pd—S bond to the other Pd atom, and the other two benzothiazolethiolate units are bonded to the same Pd atoms by, respectively, a Pd—S and a Pd—N bond. In (II), three benzothiazolethiolate units are bonded by a Pd—N bond to one Pd atom and by a Pd—S bond to the other Pd atom, and the fourth benzothiazolethiolate unit is bonded to the same Pd atoms by, respectively, a Pd—S bond and a Pd—N bond.     

Structure and stability of (CuNO) isomers

Quantum-mechanical calculations have been performed on various isomers of the (CuNO)⁺ system. A ²Π ground state is found for the linear CuNO⁺ and CuON⁺ isomers and a ²A′ state for the bent CuNO⁺ and CuON⁺ isomers. Energy calculations indicate that the linear CuNO⁺ structure is the most stable, the bent CuNO⁺ and CuON⁺ and the linear CuON⁺ structures are at 0.86 eV, 0.99 eV and 1.04 eV above this respectively. In the CuNO⁺ → CuON⁺ interconversion between the linear isomers, three transition states are involved, whereas the bent CuNO⁺ isomer is found to be an intermediate species. The isomerization barriers, dissociation energies, equilibrium geometries and vibration frequencies are given for all isomers in their ground and first excited states.     

Low-lying isomers and finite temperature behavior of (H2O)6 -

(H2O)(6) (-) appears as a "magic" number water cluster in (H2O)(n) (-) mass spectra. The structure of the (H2O)(6) (-) isomer dominating the experimental population has been established only recently [N. I. Hammer et al., J. Phys. Chem. A 109, 7896 (2005)], and the most noteworthy characteristic of this isomer is the localization of the excess electron in the vicinity of a double-acceptor monomer. In the present work, we use a quantum Drude model to characterize the low-energy isomers and the finite temperature properties of (H2O)(6) (-). Comparison with ab initio calculations shows that the use of a water model employing distributed polarizabilities and distributed repulsive sites is necessary to correctly reproduce the energy ordering of the low-lying isomers. Both the simulations and the ab initio calculations predict that there are several isomers of (H2O)(6) (-) significantly lower in energy than the experimentally observed species, suggesting that the experimental distribution is far from equilibrium.     

Syntheses of the linkage isomers (H2O)5CrNCCo(CN)5 and (H2O)5CrCNCo(CN)5

The slow reaction of Cr(H₂O)₆³⁺ with Co(CN)₆³⁻ produces (H₂O)CrNCCo(CN)₅. The rapid reaction of Co(CN)₅N₃³⁻ with nitrious acid in the presence of Cr)OH₂)₅CN²⁺ produces (H₂O)₅CrCNCo(CN)₅. The two binuclear complexes were separated and purified by cation and anion exchange procedures. The orientation of the bridging cyanide in the isomeric complexes was determined by a spectroscopic technique. For (H₂O)₅CrNCCo(CN)₅ the ⁴A_2g → ⁴T_2g and ⁴A_2g → ⁴T_1g of the chromium moiety are at 560 and 401 nm, respectively, and the ¹A_1g → ¹T_1g of the cobalt moiety is at 310 nm. For (H₂O)₅CrCNCo(CN)₅ the ⁴A_2g → ⁴T_2g band is at 552 nm, but the ⁴A_2g → ⁴T_1g absorption of the chromium is obscured by the ¹A_1g → ¹T_1g transition of the cobalt at 347 nm. The base hydrolysis of (H₂O)₅CNCCo(CN)₅ produces Co(CN)₆³⁻ and “chromite” quantitatively. The vase hydrolysis of (H₂O)₅CrCNCo(CN)₅ produces chromite and an unidentified cobalt(III) species that absorbs at 345–347 nm.     

Computational study of the release of H2 from ammonia borane dimer (BH3NH3)2 and its ion pair isomers

High-level electronic structure calculations have been used to map out the relevant portions of the potential energy surfaces for the release of H2 from dimers of ammonia borane, BH3NH3 (AB). Using the correlation-consistent aug-cc-pVTZ basis set at the second-order perturbation MP2 level, geometries of stationary points were optimized. Relative energies were computed at these points using coupled-cluster CCSD(T) theory with the correlation-consistent basis sets at least up to the aug-cc-pVTZ level and in some cases extrapolated to the complete basis set limit. The results show that there are a number of possible dimers involving different types of hydrogen-bonded interactions. The most stable gaseous phase (AB)2 dimer results from a head-to-tail cyclic conformation and is stabilized by 14.0 kcal/mol with respect to two AB monomers. (AB)2 can generate one or two H2 molecules via several direct pathways with energy barriers ranging from 44 to 50 kcal/mol. The diammoniate of diborane ion pair isomer, [BH4-][NH3BH2NH3+] (DADB), is 10.6 kcal/mol less stable than (AB)2 and can be formed from two AB monomers by overcoming an energy barrier of approximately 26 kcal/mol. DADB can also be generated from successive additions of two NH3 molecules to B2H6 and from condensation of AB with separated BH3 and NH3 molecules. The pathway for H2 elimination from DADB is characterized by a smaller energy barrier of 20.1 kcal/mol. The alternative ion pair [NH4+][BH3NH2BH3-] is calculated to be 16.4 kcal/mol above (AB)2 and undergoes H2 release with an energy barrier of 17.7 kcal/mol. H2 elimination from both ion pair isomers yields the chain BH3NH2BH2NH3 as product. Our results suggest that the neutral dimer will play a minor role in the release of H2 from ammonia borane, with a dominant role from the ion pairs as observed experimentally in ionic liquids and the solid state.     

Structural isomers in a 2-(5-bromo-2-pyridylazo)-5diethylaminophenolatochloropalladium(II) crystal.

Crystal structure of 2-(5-bromo-2-pyridylazo)-5-diethylaminophenolatochloropalladium(II) (PdLCl) has been determined by X-ray diffraction. A crystal of PdLCl was constructed by two structural isomers of PdLCl molecules, which were particularly different in the positions of the carbon atoms at the diethylamino group, having cis-like or trans-like conformation for the carbon atoms. The molecules of PdLCl in the crystal were warped by a steric hindrance of the diethylamino group.     

4(And 5)-cyclopropylamino-5(and 4)halo-3(2H)pyridazinones. Formation and characterization of isomers

The reactions of 4,5-dihalo-3(2H)pyridazinones with ammonia and amines gave mixtures of 5-amino-4-halo- and 4-amino-5-halo-3(2H)pyridazinones separated by chromatography. Structures were elucidated by means of retention values (R_f) and confirmed by independent synthesis.     

Experimental thermochemical study of two 2-alkylbenzimidazole isomers (alkyl=propyl and isopropyl)

This paper reports the values of the standard (p^∘=0.1 MPa) molar enthalpy of formation in the condensed, at T=298.15 K, for 2-R-benzimidazoles (R=propyl, isopropyl), derived from, the respective enthalpies of combustion in oxygen, measured by static bomb combustion calorimetry and the standard molar enthalpies of sublimation, at T=298.15 K, obtained using Calvet microcalorimetry in the case of 2-isopropylbenzimidazole and, by the variation of vapour pressures, determined by the Knudsen effusion technique, with temperatures between (344 and 365) K for 2-propylbenzimidazole. Heat capacities, in the temperature ranges from T=268 K to near their respective melting temperatures, T=421 K for 2-propylbenzimidazole and T=464 K for 2-isopropylbenzimidazole, were measured with a differential scanning calorimeter. These values were used to derive the standard molar enthalpies of formation, of the two 2-benzimidazole derivatives, in gaseous phase.     

Dichlorobis(2-phenylazopyridine)ruthenium(II) complexes: characterisation, spectroscopic and structural properties of four isomers

The didentate ligand 2-phenylazopyridine (azpy) can--in theory--give rise to five different isomeric complexes of the type [Ru(azpy)2Cl2], of which three have been known since 1980. The molecular structures of the cis-dichlorobis(2-phenylazopyridine) ruthenium(II) complexes alpha-[Ru(azpy)2Cl2] and beta-[Ru(azpy)2Cl2](in which the coordinating pyridine nitrogen atoms are in mutually trans and cis positions, respectively, whilst the azo nitrogen atoms are in mutually cis positions) were unambiguously determined in the early 1980s. The third isomer, gamma-[Ru(azpy)2Cl2], has for two decades, erroneously, been assumed to be the all-trans isomer. In a recent communication we have proven that for this gamma isomer the chloride ions are indeed in a trans geometry, but the pyridine nitrogen and azo nitrogen atoms of the two azpy ligands are in mutually cis geometries. In this paper the isolation of a fourth isomer is presented, the hitherto unknown delta-[Ru(azpy)2Cl2]. The isomeric structure of delta-[Ru(azpy)2Cl2] has been determined by 1H-NMR spectroscopy and single-crystal X-ray diffraction analysis, and is the all-trans isomer. The bis(azpy)-ruthenium(II) isomers are of interest because of the pronounced cytotoxicity they exhibit against tumour cell lines and could be very useful in the search for structure-activity relationships of antitumour-active ruthenium complexes, as among the isomers there is a significant difference in activity. It is of paramount importance to have a good understanding of the structural and spectroscopic properties of these complexes, which in this paper are compared and discussed, with a particular emphasis on 1D and 2D 1H NMR spectroscopies.     

Infrared spectra of C(3)H(3)(+)-N(2) dimers: identification of proton-bound c-C(3)H(3)(+)-N(2) and H(2)CCCH(+)-N(2) isomers.

Mid-infrared photodissociation spectra of mass selected C(3)H(3)(+)-N(2) ionic complexes are obtained in the vicinity of the C-H stretch fundamentals (2970-3370 cm(-1)). The C(3)H(3)(+)-N(2) dimers are produced in an electron impact cluster ion source by supersonically expanding a gas mixture of allene, N(2), and Ar. Rovibrational analysis of the spectra demonstrates that (at least) two C(3)H(3)(+) isomers are produced in the employed ion source, namely the cyclopropenyl (c-C(3)H(3)(+)) and the propargyl (H(2)CCCH(+)) cations. This observation is the first spectroscopic detection of the important c-C(3)H(3)(+) ion in the gas phase. Both C(3)H(3)(+) cations form intermolecular proton bonds to the N(2) ligand with a linear -C-H...N-N configuration, leading to planar C(3)H(3)(+)-N(2) structures with C(2v) symmetry. The strongest absorption of the H(2)CCCH(+)-N(2) dimer in the spectral range investigated corresponds to the acetylenic C-H stretch fundamental (v(1) = 3139 cm(-1)), which experiences a large red shift upon N(2) complexation (Delta(v1) approximately -180 cm(-1)). For c-C(3)H(3)(+)-N(2), the strongly IR active degenerate antisymmetric stretch vibration (v4)) of c-C(3)H(3)(+) is split into two components upon complexation with N(2): v4)(a(1)) = 3094 cm(-1) and v4)(b(2)) = 3129 cm(-1). These values bracket the yet unknown v4) frequency of free c-C(3)H(3)(+) in the gas phase, which is estimated as 3125 +/- 4 cm(-1) by comparison with theoretical data. Analysis of the nuclear spin statistical weights and A rotational constants of H(2)CCCH(+)-N(2) and c-C(3)H(3)(+)-N(2) provide for the first time high-resolution spectroscopic evidence that H(2)CCCH(+) and c-C(3)H(3)(+) are planar ions with C(2v) and D(3h) symmetry, respectively. Ab initio calculations at the MP2(full)/6-311G(2df,2pd) level confirm the given assignments and predict intermolecular separations of R(e) = 2.1772 and 2.0916 A and binding energies of D(e) = 1227 and 1373 cm(-1) for the H-bound c-C(3)H(3)(+)-N(2) and H(2)CCCH(+)-N(2) dimers, respectively.