The effect of selfassociation of mercurated carbonyl compounds of mercury-199 chemical shifts

Temperature and concentration dependences of mercury-199 chemical shifts in benzene solutions of bis(methylethylketone)mercury Hg(CH₂COC₂H₅) (I) and α-bis(methylacetoacetone)mercury Hg(CH₂COCH₂COOCH₃)₂ (II) are determined by the ¹H-{¹⁹⁹Hg}method. The NMR data obtained and the IR spectra are indicative of selfassociation of I and II in solution with the formation of weak intermolecular coordination bonds Hg ← :OC. The enthalpies of complex formation calculated on the assumption of one mercury atom bonding with only one carbonyl function are equal to ?3.2 ± 0.1 kcal/mol and ?2.2 ± 0.1 kcal/mol for I and II, respectively.     

The dynamic structure of <Emphasis Type="Italic">cis</Emphasis> and <Emphasis Type="Italic">trans</Emphasis> conformers of substituted phosphinous acids

The potential energy surfaces of bis-(trifluoromethyl)-phosphinous (III), diemthylphosphinous (IV), and bis-(pentafluorophenyl)-phosphinous (V) acids, the geometric parameters of the cis and trans conformers of these acids, and their P-O and O-H stretching vibration frequencies were calculated by the density functional theory method (PBE, 4Z). The potential energy surface sections corresponding to internal rotations about the P-O bonds were constructed, and dynamic problems for such a motion of the proton in a cyclic potential were solved by the Ritz method using a basis set of 100 trigonometric functions. According to calculations, the energy differences between the cis and trans conformers of acids III–V were of 4–7 kJ/mol, and the heights of potential barriers separating these conformers were of from 11 to 16 kJ/mol. In acids III and V, the cis, and, in IV, the trans conformer was stabler. At 298 K, only the ground vibrational states were populated for both rotamers of IV and V and the cis conformer of III. The special features of the potential of III were such that, at 298 K, the first excited vibrational level of its trans conformer was also noticeably populated.     

Raman Scattering Study of Natural and Synthetic Compounds Containing Polyene Chains

Doklady Physics - The dependence of Raman spectra of the molecules containing polyene chains on the conjugation length, structure of side and end groups, and isomer type is analyzed theoretically.     

Photochemical reactions of di(naphthyl-1-methyl)mercury in various solvents

It was found that the photolysis of di(naphthyl-1-methyl)mercury (1) gives 1,2-dinaphthylethane (2) in heptane and benzene solvents and 2 and 1-methylnaphthalene in isopropanol and acetonitrile. Irradiation of 1 in carbon tetrachloride gives 2 and ClHgCH₂C₁₀H₇ as primary reaction products, while the chloride is further photolyzed to 2. Quantum yields of the photolysis of 1 are high and equal to unity almost for all solvents. The chloride photodecomposition yield is an order of magnitude lower (0.1).     

Electroreduction of cationic fluorene complexes of manganese

Using cyclic voltammetry method, the reduction of cationic η⁶-fluorene complexes of manganese [(η⁶-9-R-C₁₃H₉)Mn(CO)₂L]PF₆ (L = CO, R = H (1 ⁺); L = CO, R = CH₃ (2 ⁺); L = PⁿBu₃, R = H (3 ⁺); L = CO, R = ^tBu (4 ⁺)) is studied. It is shown that, depending on the nature of a substituent in the position 9 of the fluorene ligand, the reduction occurs either with the detachment of an H atom from position 9 to give zwitterion compounds (complexes 1 ^±, 2 ^±, 3 ^±) or with the attachment of an H atom into the coordinated ring of the fluorene ligand to given η⁵-cyclohexadienyl complex (η⁵-9-^tBu-C₁₃H₉)Mn(CO)₃ (5).