Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX4(X = Cl, Br, I)/Ethyl Acetate System

H. Lars Deubner; Tim Graubner; Magnus R. Buchner; Florian Weigend; Sergei I. Ivlev; Antti J. Karttunen; Florian Kraus

doi:10.1021/acsomega.2c00175

Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX₄(X = Cl, Br, I)/Ethyl Acetate System

H. Lars Deubner, Tim Graubner, Magnus R. Buchner, Florian Weigend, Sergei I. Ivlev, Antti J. Karttunen, Florian Kraus^*

^*Tämän työn vastaava kirjoittaja

University of Marburg

Tutkimustuotos: Lehtiartikkeli › Article › Scientific › vertaisarvioitu

100 Lataukset (Pure)

Abstrakti

The reaction of the uranium(IV) halides UCl₄, UBr₄, or UI4 with ethyl acetate (EtOAc) leads to the formation of the complexes [UX₃(EtOAc)₄][UX₅(EtOAc)] (X = Cl, Br) or [UI₄(EtOAc)₃]. Thus, both UCl₄ and UBr₄ show self-ionization in ethyl acetate to a distorted pentagonal bipyramidal [UX₃(EtOAc)₄]⁺ cation and a distorted octahedral [UX₅(EtOAc)]^- anion. Surprisingly, the chloride and bromide compounds are not isotypic. While [UCl₃(EtOAc)₄][UCl₅(EtOAc)] crystallizes in the orthorhombic crystal system, space group P2₁2₁2₁ at 250 K, the bromide compound crystallizes in the monoclinic crystal system, P12₁/n1 at 100 K. Unexpectedly, UI₄ does not show self-ionization but forms [UI₄(EtOAc)₃] molecules, which crystallize in the monoclinic crystal system, P2₁/c, at 100 K. The compounds were characterized by single-crystal X-ray diffraction, IR, Raman, and NMR spectroscopy, as well as molecular quantum chemical calculations using solvent models.

Alkuperäiskieli	Englanti
Sivut	11995–12003
Sivumäärä	9
Julkaisu	ACS Omega
Vuosikerta	7
Numero	14
Varhainen verkossa julkaisun päivämäärä	1 huhtik. 2022
DOI - pysyväislinkit	https://doi.org/10.1021/acsomega.2c00175
Tila	Julkaistu - 12 huhtik. 2022
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Pääsy asiakirjaan

10.1021/acsomega.2c00175Lisenssi: CC BY-NC-ND

CHEM_Deubner_et_al_Surprises_in_the_Solvent-Induced_2022_ACS_OmegaFinal published version, 1,37 MBLisenssi: CC BY-NC-ND

Muut tiedostot ja linkit

Linkki julkaisuun Scopuksessa

CCDC 2124221: Experimental Crystal Structure Determination
Deubner, H. L. (Contributor), Graubner, T. (Contributor), Buchner, M. R. (Contributor), Weigend, F. (Contributor), Ivlev, S. I. (Contributor), Karttunen, A. J. (Creator) & Kraus, F. (Contributor), Cambridge Crystallographic Data Centre , 1 tammik. 2022
DOI - pysyväislinkki: 10.5517/ccdc.csd.cc299f8b, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc299f8b&sid=DataCite
Tietoaineisto: Dataset
CCDC 2124219: Experimental Crystal Structure Determination
Deubner, H. L. (Contributor), Graubner, T. (Contributor), Buchner, M. R. (Contributor), Weigend, F. (Contributor), Ivlev, S. I. (Contributor), Karttunen, A. J. (Creator) & Kraus, F. (Contributor), Cambridge Crystallographic Data Centre , 1 tammik. 2022
DOI - pysyväislinkki: 10.5517/ccdc.csd.cc299f68, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc299f68&sid=DataCite
Tietoaineisto: Dataset
CCDC 2124220: Experimental Crystal Structure Determination
Deubner, H. L. (Contributor), Graubner, T. (Contributor), Buchner, M. R. (Contributor), Weigend, F. (Contributor), Ivlev, S. I. (Contributor), Karttunen, A. J. (Creator) & Kraus, F. (Contributor), Cambridge Crystallographic Data Centre , 1 tammik. 2022
DOI - pysyväislinkki: 10.5517/ccdc.csd.cc299f79, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc299f79&sid=DataCite
Tietoaineisto: Dataset

Siteeraa tätä

@article{fa772d6e1ed44c37b901ff8707f72cc2,

title = "Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX4(X = Cl, Br, I)/Ethyl Acetate System",

abstract = "The reaction of the uranium(IV) halides UCl4, UBr4, or UI4 with ethyl acetate (EtOAc) leads to the formation of the complexes [UX3(EtOAc)4][UX5(EtOAc)] (X = Cl, Br) or [UI4(EtOAc)3]. Thus, both UCl4 and UBr4 show self-ionization in ethyl acetate to a distorted pentagonal bipyramidal [UX3(EtOAc)4]+ cation and a distorted octahedral [UX5(EtOAc)]- anion. Surprisingly, the chloride and bromide compounds are not isotypic. While [UCl3(EtOAc)4][UCl5(EtOAc)] crystallizes in the orthorhombic crystal system, space group P212121 at 250 K, the bromide compound crystallizes in the monoclinic crystal system, P121/n1 at 100 K. Unexpectedly, UI4 does not show self-ionization but forms [UI4(EtOAc)3] molecules, which crystallize in the monoclinic crystal system, P21/c, at 100 K. The compounds were characterized by single-crystal X-ray diffraction, IR, Raman, and NMR spectroscopy, as well as molecular quantum chemical calculations using solvent models.",

author = "Deubner, {H. Lars} and Tim Graubner and Buchner, {Magnus R.} and Florian Weigend and Ivlev, {Sergei I.} and Karttunen, {Antti J.} and Florian Kraus",

note = "Funding Information: We thank the Deutsche Forschungsgemeinschaft for funding. T.G. thanks the HPC-EUROPA3 (INFRAIA-2016-1-730897) for a travel grant and the computing resources provided by CSC, the Finnish IT Center for Science. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

month = apr,

day = "12",

doi = "10.1021/acsomega.2c00175",

language = "English",

volume = "7",

pages = "11995–12003",

journal = "ACS Omega",

issn = "2470-1343",

publisher = "American Chemical Society",

number = "14",

}

TY - JOUR

T1 - Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX4(X = Cl, Br, I)/Ethyl Acetate System

AU - Deubner, H. Lars

AU - Graubner, Tim

AU - Buchner, Magnus R.

AU - Weigend, Florian

AU - Ivlev, Sergei I.

AU - Karttunen, Antti J.

AU - Kraus, Florian

N1 - Funding Information: We thank the Deutsche Forschungsgemeinschaft for funding. T.G. thanks the HPC-EUROPA3 (INFRAIA-2016-1-730897) for a travel grant and the computing resources provided by CSC, the Finnish IT Center for Science. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/4/12

Y1 - 2022/4/12

N2 - The reaction of the uranium(IV) halides UCl4, UBr4, or UI4 with ethyl acetate (EtOAc) leads to the formation of the complexes [UX3(EtOAc)4][UX5(EtOAc)] (X = Cl, Br) or [UI4(EtOAc)3]. Thus, both UCl4 and UBr4 show self-ionization in ethyl acetate to a distorted pentagonal bipyramidal [UX3(EtOAc)4]+ cation and a distorted octahedral [UX5(EtOAc)]- anion. Surprisingly, the chloride and bromide compounds are not isotypic. While [UCl3(EtOAc)4][UCl5(EtOAc)] crystallizes in the orthorhombic crystal system, space group P212121 at 250 K, the bromide compound crystallizes in the monoclinic crystal system, P121/n1 at 100 K. Unexpectedly, UI4 does not show self-ionization but forms [UI4(EtOAc)3] molecules, which crystallize in the monoclinic crystal system, P21/c, at 100 K. The compounds were characterized by single-crystal X-ray diffraction, IR, Raman, and NMR spectroscopy, as well as molecular quantum chemical calculations using solvent models.

AB - The reaction of the uranium(IV) halides UCl4, UBr4, or UI4 with ethyl acetate (EtOAc) leads to the formation of the complexes [UX3(EtOAc)4][UX5(EtOAc)] (X = Cl, Br) or [UI4(EtOAc)3]. Thus, both UCl4 and UBr4 show self-ionization in ethyl acetate to a distorted pentagonal bipyramidal [UX3(EtOAc)4]+ cation and a distorted octahedral [UX5(EtOAc)]- anion. Surprisingly, the chloride and bromide compounds are not isotypic. While [UCl3(EtOAc)4][UCl5(EtOAc)] crystallizes in the orthorhombic crystal system, space group P212121 at 250 K, the bromide compound crystallizes in the monoclinic crystal system, P121/n1 at 100 K. Unexpectedly, UI4 does not show self-ionization but forms [UI4(EtOAc)3] molecules, which crystallize in the monoclinic crystal system, P21/c, at 100 K. The compounds were characterized by single-crystal X-ray diffraction, IR, Raman, and NMR spectroscopy, as well as molecular quantum chemical calculations using solvent models.

UR - http://www.scopus.com/inward/record.url?scp=85128283952&partnerID=8YFLogxK

U2 - 10.1021/acsomega.2c00175

DO - 10.1021/acsomega.2c00175

M3 - Article

AN - SCOPUS:85128283952

SN - 2470-1343

VL - 7

SP - 11995

EP - 12003

JO - ACS Omega

JF - ACS Omega

IS - 14

ER -

Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX4(X = Cl, Br, I)/Ethyl Acetate System

Abstrakti

Pääsy asiakirjaan

Muut tiedostot ja linkit

Sormenjälki

Tietoaineistot

CCDC 2124221: Experimental Crystal Structure Determination

CCDC 2124219: Experimental Crystal Structure Determination

CCDC 2124220: Experimental Crystal Structure Determination

Siteeraa tätä

Surprises in the Solvent-Induced Self-Ionization in the Uranium Tetrahalide UX₄(X = Cl, Br, I)/Ethyl Acetate System