Uranyl Halides from Liquid Ammonia: [UO2(NH3)(5)]Cl-2 center dot NH3 and [UO2F2(NH3)(3)](2)center dot 2NH(3) and Their Decomposition Products [UO2Cl2(NH3)(3)] and [UO2F2(NH3)(3)]

Patrick Woidy, Antti J. Karttunen, Florian Kraus*

*Tämän työn vastaava kirjoittaja

Tutkimustuotos: LehtiartikkeliArticleScientificvertaisarvioitu

Abstrakti

Uranyl chloride UO2Cl2 and uranyl fluoride UO2F2 react with dry liquid ammonia under the formation of traffic-green crystals of pentaammine dioxido uranium(VI) dichloride ammonia (1/1) [UO2(NH3)5]Cl2 center dot NH3 (1) and sulfur-yellow crystals of triammine difluorido dioxido uranium(VI) ammonia (2/2) [UO2F2(NH3)3]2 center dot 2NH3 (2), respectively. Low-temperature X-ray structure analyses on single crystals of the two compounds were conducted. Compound 1 crystallizes in the orthorhombic space group Cmcm with a = 12.7865(2), b = 10.5106(2), c = 8.7089(2) angstrom, V = 1170.45(4) angstrom 3 at 123 K with Z = 4. Compound 2 crystallizes in the orthorhombic space group Pnma with a = 20.8451(5), b = 9.1267(2), c = 8.3371(2) angstrom, V = 1586(6) angstrom 3 at 123 K with Z = 4. Further investigations on the room-temperature decomposition products of compounds 1 and 2 by Raman and IR spectroscopy, TGA MS and X-ray powder diffraction measurements and deuteration studies led to the identification of triammine dichlorido dioxido uranium(VI) UO2Cl2(NH3)3 (3) and triammine difluorido dioxido uranium(VI) UO2F2(NH3)3 (4) in the form of fern-green and zinc-yellow powders. Quantum chemical studies at the DFT-PBE0/TZVP level of theory support the experimental observations andalso show that the O=U=O triple bonding in the [UO2F2(NH3)3] molecule of compound 2 is weaker in comparison to the one in the [UO2(NH3)5]2+ dication of compound 1.

AlkuperäiskieliEnglanti
Sivut2044-2052
Sivumäärä9
JulkaisuZeitschrift fur Anorganische und Allgemeine Chemie
Vuosikerta638
Numero12-13
DOI - pysyväislinkit
TilaJulkaistu - lokakuuta 2012
OKM-julkaisutyyppiA1 Julkaistu artikkeli, soviteltu

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