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

doi:10.1002/zaac.201200127

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^*

^*Corresponding author for this work

Not published at Aalto University

Research output: Contribution to journal › Article › Scientific › peer-review

Abstract

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.

Original language	English
Pages (from-to)	2044-2052
Number of pages	9
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Volume	638
Issue number	12-13
DOIs	https://doi.org/10.1002/zaac.201200127
Publication status	Published - Oct 2012
MoE publication type	A1 Journal article-refereed

Funding

A. J. K. gratefully acknowledges financial support from the Academy of Finland (grant 138560/2010). F. K. would like to thank the Fonds der Chemischen Industrie for his Liebig Stipend and the Deutsche Forschungsgemeinschaft for his Heisenberg Fellowship. The Deutsche Forschungsgemeinschaft is acknowledged for the uranium grant. P. W. would like to thank the TUM Graduate School. Prof. Dr. A. Kornath, Munich, is acknowledged for allowing us to perform measurements on his Raman spectrometer, Prof. Dr. O. Hinrichsen for use of the thermogravimetric analysis instrument. We thank Prof. Dr. B. G. Muller, Giessen, and Prof. Dr. R. Hoppe, Giessen, for the kind donation of many chemicals and equipment.

Keywords

Uranyl
Halides
Liquid ammonia
X-ray diffraction
Ab initio calculations
CRYSTAL-STRUCTURE
POPULATION ANALYSIS
INFRARED-SPECTRA
BASIS-SETS
URANIUM
RAMAN
PSEUDOPOTENTIALS
COMPLEXES
CHLORIDE
NITRATE

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10.1002/zaac.201200127

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@article{d5a487ad1b414db280898a965f734501,

title = "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)]",

abstract = "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.",

keywords = "Uranyl, Halides, Liquid ammonia, X-ray diffraction, Ab initio calculations, CRYSTAL-STRUCTURE, POPULATION ANALYSIS, INFRARED-SPECTRA, BASIS-SETS, URANIUM, RAMAN, PSEUDOPOTENTIALS, COMPLEXES, CHLORIDE, NITRATE",

author = "Patrick Woidy and Karttunen, \{Antti J.\} and Florian Kraus",

year = "2012",

month = oct,

doi = "10.1002/zaac.201200127",

language = "English",

volume = "638",

pages = "2044--2052",

journal = "Zeitschrift fur Anorganische und Allgemeine Chemie",

issn = "0044-2313",

publisher = "Wiley",

number = "12-13",

}

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)]. / Woidy, Patrick; Karttunen, Antti J.; Kraus, Florian.
In: Zeitschrift fur Anorganische und Allgemeine Chemie, Vol. 638, No. 12-13, 10.2012, p. 2044-2052.

Research output: Contribution to journal › Article › Scientific › peer-review

TY - JOUR

T1 - Uranyl Halides from Liquid Ammonia

T2 - [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)]

AU - Woidy, Patrick

AU - Karttunen, Antti J.

AU - Kraus, Florian

PY - 2012/10

Y1 - 2012/10

N2 - 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.

AB - 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.

KW - Uranyl

KW - Halides

KW - Liquid ammonia

KW - X-ray diffraction

KW - Ab initio calculations

KW - CRYSTAL-STRUCTURE

KW - POPULATION ANALYSIS

KW - INFRARED-SPECTRA

KW - BASIS-SETS

KW - URANIUM

KW - RAMAN

KW - PSEUDOPOTENTIALS

KW - COMPLEXES

KW - CHLORIDE

KW - NITRATE

U2 - 10.1002/zaac.201200127

DO - 10.1002/zaac.201200127

M3 - Article

SN - 0044-2313

VL - 638

SP - 2044

EP - 2052

JO - Zeitschrift fur Anorganische und Allgemeine Chemie

JF - Zeitschrift fur Anorganische und Allgemeine Chemie

IS - 12-13

ER -

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)]

Abstract

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Keywords

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