Stereospecificity of 1H, 13C and 15N shielding constants in the isomers of methylglyoxal bisdimethylhydrazone: problem with configurational assignment based on 1H chemical shifts

In the ¹³C NMR spectra of methylglyoxal bisdimethylhydrazone, the ¹³C‐5 signal is shifted to higher frequencies, while the ¹³C‐6 signal is shifted to lower frequencies on going from the EE to ZE isomer following the trend found previously. Surprisingly, the ¹H‐6 chemical shift and ¹J(C‐6,H‐6) coupling constant are noticeably larger in the ZE isomer than in the EE isomer, although the configuration around the –CH═N– bond does not change. This paradox can be rationalized by the C–H?N intramolecular hydrogen bond in the ZE isomer, which is found from the quantum‐chemical calculations including Bader's quantum theory of atoms in molecules analysis. This hydrogen bond results in the increase of δ(¹H‐6) and ¹J(C‐6,H‐6) parameters. The effect of the C–H?N hydrogen bond on the ¹H shielding and one‐bond ¹³C–¹H coupling complicates the configurational assignment of the considered compound because of these spectral parameters. The ¹H, ¹³C and ¹⁵N chemical shifts of the 2‐ and 8‐(CH₃)₂N groups attached to the –C(CH₃)═N– and –CH═N– moieties, respectively, reveal pronounced difference. The ab initio calculations show that the 8‐(CH₃)₂N group conjugate effectively with the π‐framework, and the 2‐(CH₃)₂N group twisted out from the plane of the backbone and loses conjugation. As a result, the degree of charge transfer from the N‐2– and N‐8– nitrogen lone pairs to the π‐framework varies, which affects the ¹H, ¹³C and ¹⁵N shieldings. Copyright © 2012 John Wiley & Sons, Ltd.     

Low temperature nuclear orientation of239Np in gadolinium host

The angular distribution of γ-radiation from the decay of²³⁹Np oriented at low temperatures in gadolinium host was investigated. The orientation parameters B2 and B4 were determined. The attenuation factors for two long-living states in²³⁹Pu at 391.5 keV and 285.4 keV were calculated. From the anisotropies measured the multipole mixing ratios for 11 gamma-transitions in²³⁹Pu were deduced. The results obtained support the assignment of spins of the levels at 492.2 keV and 391.6 keV as 3/2⁻ and 7/2⁻, respectively.     

Influence of Crystallization Conditions in Production of Citric Acid on the Properties of Forming Calcium Sulfate

The boundaries of phase equilibria involving calcium sulfate crystal hydrates in a citric acid solution were calculated. The influence exerted by an excess amount of sulfuric acid on the stability of calcium sulfate crystal hydrates in citric acid solutions was considered. The possibility of achieving a hemihydrate mode of citric acid extraction from calcium citrate was studied.