Isocyanide adducts of tri- and tetravalent uranium metallocenes supported by tetra(isopropyl)cyclopentadienyl ligands. Issue 34 (19th August 2020)

• Record Type: Journal Article
• Authors: Boreen, Michael A.; Groß, Oliver A.; Hohloch, Stephan; Arnold, John
• Is Part Of: Dalton transactions. Volume 49:Issue 34(2020)
• Page Start: 11971
• Page End: 11977
• Publication Date: 2020-08-19
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d0dt02005b
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Reactions of uranium(iii ) metallocenium salt [(Cp iPr4 )2 U][B(C6 F5 )4 ] with tert -butyl isocyanide yielded cationic uranium(iv ) products, including a rare example of a linear f-block metallocene complex. Abstract : Reaction of the uranium(iii ) metallocenium salt [(Cp iPr4 )2 U][B(C6 F5 )4 ] with tert -butyl isocyanide ( t BuNC) yielded the dicationic uranium(iv ) complex [(Cp iPr4 )2 U(CN t Bu)4 ][B(C6 F5 )4 ]2 (1 ), which displays a linear metallocene geometry. Use of crude mixtures of [(Cp iPr4 )2 U][B(C6 F5 )4 ], which contain a soluble source of iodide, led instead to isolation of the monocationic uranium(iv ) iodide complex [(Cp iPr4 )2 U(I)(CN t Bu)2 ][B(C6 F5 )4 ] (2 ). Adduct formation with no change in oxidation state was observed upon addition of t BuNC to the neutral uranium(iii ) species (Cp iPr4 )2 UI, resulting in isolation of (Cp iPr4 )2 U(I)(CN t Bu) (3 ). X-ray crystallographic and IR spectroscopic studies both showed effects ascribed to the presence of multiple strongly donating isocyanide ligands in 1 .