A Comparative IRMPD and DFT Study of Fe3+ and UO2(2+) Complexation with N-methylacetohydroxamic Acid
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F18%3A10374843" target="_blank" >RIV/00216208:11310/18:10374843 - isvavai.cz</a>
Výsledek na webu
<a href="https://doi.org/10.1021/acs.inorgchem.7b02567" target="_blank" >https://doi.org/10.1021/acs.inorgchem.7b02567</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.7b02567" target="_blank" >10.1021/acs.inorgchem.7b02567</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
A Comparative IRMPD and DFT Study of Fe3+ and UO2(2+) Complexation with N-methylacetohydroxamic Acid
Popis výsledku v původním jazyce
Iron(III) and uranyl complexes of N-methylacetohydroxamic acid (NMAH) have been investigated by mass spectrometry, infrared multiphoton dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. A comparison between IRMPD and theoretical IR spectra enabled one to probe the structures for some selected complexes detected in the gas phase. The results show that coordination of Fe3+ and UO2(2+) by hydroxamic acid is of a very similar nature. Natural bond orbital analysis suggests that bonding in uranyl complexes possesses a slightly stronger ionic character than that in iron complexes. Collision-induced dissociation (CID), IRMPD, and O-18-labeling experiments unambiguously revealed a rare example of the U=O bond activation concomitant with the elimination of a water molecule from the gaseous [UO2(NMA)(NMAH)(2)](+) complex. The U=O bond activation is observed only for complexes with one monodentate NMAH molecule forming a hydrogen bond toward one "yl" oxygen atom, as was found by DFT calculations. This reactivity might explain oxygen exchange observed for uranyl complexes.
Název v anglickém jazyce
A Comparative IRMPD and DFT Study of Fe3+ and UO2(2+) Complexation with N-methylacetohydroxamic Acid
Popis výsledku anglicky
Iron(III) and uranyl complexes of N-methylacetohydroxamic acid (NMAH) have been investigated by mass spectrometry, infrared multiphoton dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. A comparison between IRMPD and theoretical IR spectra enabled one to probe the structures for some selected complexes detected in the gas phase. The results show that coordination of Fe3+ and UO2(2+) by hydroxamic acid is of a very similar nature. Natural bond orbital analysis suggests that bonding in uranyl complexes possesses a slightly stronger ionic character than that in iron complexes. Collision-induced dissociation (CID), IRMPD, and O-18-labeling experiments unambiguously revealed a rare example of the U=O bond activation concomitant with the elimination of a water molecule from the gaseous [UO2(NMA)(NMAH)(2)](+) complex. The U=O bond activation is observed only for complexes with one monodentate NMAH molecule forming a hydrogen bond toward one "yl" oxygen atom, as was found by DFT calculations. This reactivity might explain oxygen exchange observed for uranyl complexes.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10402 - Inorganic and nuclear chemistry
Návaznosti výsledku
Projekt
<a href="/cs/project/GA14-20077S" target="_blank" >GA14-20077S: Nehemové železné katalyzátory: výzkum reakčních mechanismů</a><br>
Návaznosti
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Ostatní
Rok uplatnění
2018
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
—
Svazek periodika
57
Číslo periodika v rámci svazku
3
Stát vydavatele periodika
US - Spojené státy americké
Počet stran výsledku
11
Strana od-do
1125-1135
Kód UT WoS článku
000424730800027
EID výsledku v databázi Scopus
2-s2.0-85041646643