Crystal structures and Mössbauer spectroscopic studies of oxo-centered trinuclear chloroacetate complexes

The crystal structures of oxo-centered trineclear cobalt-iron chloroacetate complex [Co^IIFe ₂ ^III O(CH₂ClCO₂)₆(H₂O)₃]·3H₂O (1) was compared with that of previously reported trinuclear iron complex [Fe^IIFe ₂ ^III O(CH₂ClCO₂)₆(H₂O)₃]·3H₂O (2) which has an isomorphous structure to 1. Compound 1 crystallizes in space group P2₁/n with Z=4 in a unit cell of a=14.826 (4) Å, b=4.536 (8) Å, c=14.000 (4) Å, =100.32 (2)⁰ and V=2968 (11) ų. The structure was refined to R=0.75 and R_w=0.82. The coordination geometries of the three iron atoms are observed equivalent in 1 indicating a static disorder of the position among cobalt and iron atoms. Two distinct Fe^III doublets observed in Mössbauer spectra of 1 become an indistinguishable broad doublet by dehydration of crystal water. On the other hand, no significant line-broadening is observed after the dehydration in complex 2. The results indicate that the dehydration in 2 induces a local environmental change reordering of an electronic configuration around iron atoms, whereas the remaining disordering is reflected in Mössbauer spectrum after the dehydration in 1.     

Hydrolysis of dimethyl 1-acetoxy-2,2,2-trichloroethyl phosphonate

Conclusions The hydrolysis of chloroacetophos in water includes the parallel cleavage of acetic acid, hydrochloric acid and methanol. The ratio of the products, formed in the parallel steps, was determined, and we also determined the total rate constant for the hydrolysis of chloroacetophos.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2336–2338, October, 1971.     

Sorption of butane, propane, ethane, methane, and carbon dioxide on asphaltene

Isotherms of sorption of butane, propane, ethane, methane, and carbon dioxide on an asphaltene sample of known elemental composition were measured. The effect of the pressure and temperature on the shape the sorption isotherms for all the adsorption systems studied was examined. The values of the initial heat of sorption were determined and compared to the energies of interaction of the molecules with asphaltene. The results obtained suggest that asphaltene is a swellable amorphous sorbent.     

Crystal and molecular structures of 2,10-diacetoxy-13-thiabicyclo[7.3.1]-cis-tridec-5-ene and 2,9-dichloro-13-thiabicyclo[8.2.1]-cis-tridec-5-ene sulfoxide

The crystal and molecular structures of 2,10-diacetoxy-13-thiabicyclo[7.3.1]-cis-tridec-5-ene and 2,9-dichloro-13-thiablcyclo[8.2.1]-cis-tridec-5-ene sulfoxide were established. The conformations of the molecules are such that the unshared pairs of electrons of the sulfur atoms are directed to the carboncarbon double bonds of their molecules. It was observed that there are stereochemical conditions for transannular transformations under the influence of polarized molecules and cations.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1628–1632, December, 1977.