Abstrakti
The aqueous chemistry of uranium is dominated by the linear uranyl cation [UO2]2+, yet the isoelectronic nitrogen-based analogue of this ubiquitous cation, molecular [UN2], has so far only been observed in an argon matrix. Here, we present three different complexes of [UN2] obtained by the reaction of the uranium pentahalides UCl5 or UBr5 with anhydrous liquid ammonia. The [UN2] moieties are linear, with the U atoms coordinated by five additional ligands (ammonia, chloride or bromide), resulting in a pentagonal bipyramidal coordination sphere that is also commonly adopted by the uranyl cation [UO2(L)5]2+ (L, ligand). In all three cases, the nitrido ligands are further coordinated through their lone pairs by the Lewis-acidic ligands [U(NH3)8]4+ to form almost linear, trinuclear complex cations. Those were characterized by single-crystal X-ray diffraction, Raman and infrared spectroscopy, 14N/15N isotope studies and quantum chemical calculations, which support the presence of two U≡N triple bonds within the [UN2] moieties. [Figure not available: see fulltext.]
Alkuperäiskieli | Englanti |
---|---|
Sivut | 962-967 |
Sivumäärä | 6 |
Julkaisu | Nature Chemistry |
Vuosikerta | 12 |
Numero | 10 |
Varhainen verkossa julkaisun päivämäärä | 3 elok. 2020 |
DOI - pysyväislinkit | |
Tila | Julkaistu - 1 lokak. 2020 |
OKM-julkaisutyyppi | A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä |
Sormenjälki
Sukella tutkimusaiheisiin 'Complexes featuring a linear [N≡U≡N] core isoelectronic to the uranyl cation'. Ne muodostavat yhdessä ainutlaatuisen sormenjäljen.Tietoaineistot
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CCDC 1984956: Experimental Crystal Structure Determination
Rudel, S. S. (Creator), Deubner, H. L. (Creator), Müller, M. (Creator), Karttunen, A. (Creator) & Kraus, F. (Creator), Cambridge Crystallographic Data Centre , 2020
DOI - pysyväislinkki: 10.25505/fiz.icsd.cc24mhv4
Tietoaineisto: Dataset
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CCDC 1868199: Experimental Crystal Structure Determination
Rudel, S. S. (Creator), Deubner, H. L. (Creator), Müller, M. (Creator), Karttunen, A. (Creator) & Kraus, F. (Creator), Cambridge Crystallographic Data Centre , 2020
DOI - pysyväislinkki: 10.25505/fiz.icsd.cc20q0h8
Tietoaineisto: Dataset
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CCDC 1868200: Experimental Crystal Structure Determination
Rudel, S. S. (Creator), Deubner, H. L. (Creator), Müller, M. (Creator), Karttunen, A. (Creator) & Kraus, F. (Creator), Cambridge Crystallographic Data Centre , 2020
DOI - pysyväislinkki: 10.25505/fiz.icsd.cc20q0j9
Tietoaineisto: Dataset