Linear uranium complexes X2UL5 with L=cyanide, isocyanate: DFT evidence for similarities between uranyl (X=O) and uranocene (X=Cp) derivatives

Chemistry : a European Journal
Nathalie Iché-TarratLaurent Maron

Abstract

A DFT study of the isostructural compounds [UO2L5](n-) with n=3-5 and linear [Cp2UL5](m-) with m=1-3 has been carried out for two different anionic ligands. Structurally stable structures are obtained for all systems. The coordination competition between cyanide (CN(-)) and isocyanide (NC(-)) as well as between cyanate (OCN(-)) and isocyanate (NCO(-)) has been studied in the uranyl case. A clear preference for cyanide and isocyanate complexes is reported. The coordination of five ligands in the equatorial plane is rationalised by the analysis of the MO diagram of both systems. Moreover, the qualitative comparison of the two MO diagrams shows a high similarity in agreement with the isolobality concept. The existence of linear [Cp2UL5](-) organometallic U(VI) complexes is thus proposed, as well as the possibility of obtaining complexes of both types for U(VI) and U(V) with OCN(-) ligands. In addition, the U(IV) linear metallocene is calculated to be stable for the latter ligand.

References

Oct 27, 2004·Inorganic Chemistry·Margaret-Jane CrawfordMax Suter
Jan 26, 2006·Journal of the American Chemical Society·Jérôme MaynadiéMichel Ephritikhine
Feb 1, 2007·Chemical Communications : Chem Comm·Jean-Claude BerthetMichel Ephritikhine
Feb 8, 2007·Angewandte Chemie·Jérôme MaynadiéMichel Ephritikhine

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Citations

Jun 4, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Ludovic CastroLaurent Maron
Aug 15, 2014·The Journal of Physical Chemistry. a·Michael J Van StipdonkJohn K Gibson
Mar 10, 2010·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Ludovic CastroLaurent Maron
Mar 27, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Jean-Claude BerthetMichel Ephritikhine
Jul 26, 2008·The Journal of Physical Chemistry. a·Nathalie Iché-Tarrat, Colin J Marsden
Feb 14, 2018·Inorganic Chemistry·Korey P CarterChristopher L Cahill

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