کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1317040 | 1499436 | 2015 | 12 صفحه PDF | دانلود رایگان |
• The E conformer of N-methylacetohydroxamic acid and its conjugated base prevails in water.
• The Z ⇌ E equilibrium constants for both forms have been measured by 1H NMR spectroscopy.
• The kinetic parameters for the interconversion have been measured by EXSY spectroscopy.
• Crystal structures of the mono- and bis-chelated uranyl complexes are presented.
• Both environments show characteristic IR and Raman shifts of the UO vibrational modes.
The thermodynamics and kinetics of the cis/trans isomerism of N-methylacetohydroxamic acid (NMAH) and its conjugated base (NMA−) have been reinvestigated in aqueous media by 1H NMR spectroscopy. Hindered rotation around the central C–N bond due to electronic delocalization becomes slow enough on the NMR time scale to observe both rotamers in equilibrium in D2O at room temperature. By properly assigning the methyl group resonances, evidence for the prevalence of the E over the Z form is unambiguously provided [K300 = [E] / [Z] = 2.86(2) and 9.63(5) for NMAH and NMA−, respectively], closing thereby a long-lasting dispute about the most stable conformer. To that end, calculations of the chemical shifts by density functional theory (DFT), which accurately reproduced the experimental data, turned out to be a much more reliable method than the direct computation of the relative energy for each conformer. The Z ⇌ E interconversion dynamics was probed at 300 K in D2O by 2D exchange-correlated spectroscopy (EXSY), affording the associated rate constants [kZE = 9.0(2) s− 1 and kEZ = 3.14(5) s− 1 for NMAH, kZE = 0.96(3) s− 1 and kEZ = 0.10(2) s− 1 for NMA−] and activation barriers at 300 K [ΔG≠ZE = 68.0 kJ mol− 1 and ΔG≠EZ = 70.6 kJ mol− 1 for NMAH, ΔG≠ZE = 73.6 kJ mol− 1 and ΔG≠EZ = 79.2 kJ mol− 1 for NMA−]. For the first time, mono- and bis-chelated uranium(VI) complexes of NMA− have been isolated. Crystals of [UO2(NMA)(NO3)(H2O)2] and [UO2(NMA)2(H2O)] have been characterized by X-ray diffractometry, infrared and Raman spectroscopies.
The thermodynamics and kinetics of the cis/trans isomerism exhibited by N-methylacetohydroxamic acid (NMAH) and its conjugated base (NMA−) have been investigated in aqueous media by 1H NMR and EXSY spectroscopies. The crystal structures of the [UO2(NMA)(NO3)(H2O)2] and [UO2(NMA)2(H2O)] complexes are reported together with their IR and Raman spectra.Figure optionsDownload as PowerPoint slide
Journal: Journal of Inorganic Biochemistry - Volume 151, October 2015, Pages 164–175