A Nitrido‐Centered Uranium Azido Cluster Obtained from a Uranium Azide

Abstract

Caught in the actinide: A tetranuclear azido/nitrido uranium anion containing eight end‐on bridging azido ligands and a μ4 interstitial nitrido ligand has been isolated and structurally characterized (see 1D chain; U green, Cs orange, I magenta, N blue, C white). A new two‐step procedure has been developed to promote the cluster assembly by oxidation of [UI3(thf)4] with a preformed uranium heptaazido complex.

Cation‐Mediated Conversion of the State of Charge in Uranium Arene Inverted‐Sandwich Complexes

“…72, 95, 96 This value drops off gradually with decreasing temperature to 1.26 μ B at 50 K. Below 25 K the magnetic susceptibility of complex 4 shows a temperature‐independent paramagnetism (TIP) behavior (Figure 4 d). A TIP‐only behavior is typically found in molecular U IV compounds34, 72, 95, 97, 98 and therefore the overall magnetic behavior of complex 4 is consistent with the formulation of compound 4 as a diuranium(IV) complex.…”

Stabilization of Tetravalent 4f (Ce), 5d (Hf), or 5f (Th, U) Clusters by the [α-SiW9O34]10– Polyoxometalate

“…This paramagnetic behavior agrees with a coupling of the nonmagnetic ( 3 H 4 , m J = 0) ground state with low-lying excited states. [59][60][61]65 The overall magnetic behavior is consistent with what was reported in the literature for U 4+ compounds within the localized electron model. 34 3 (SiW 9 O 34 ) 2 ] 11− ), is also arranged in a trinuclear core but with the absence of the μ 3 -O bridge, relevant to the geometry of this type of cation.…”

New Twists and Turns for Actinide Chemistry: Organometallic Infinite Coordination Polymers of Thorium Diazide

“…Although there are several transition‐metal compounds with the same structure as complex 1 , its 1D infinite chain of metal centers doubly bridged by end‐to‐end azides is a first for the actinides and is unique to thorium. As outlined in Scheme , uranium polynuclear azide compounds include the following: the previously mentioned octanuclear ring and trimer, dinuclear complexes with a single end‐to‐end azide,, 1D infinite chains of uranium and sodium singly bridged with end‐to‐end azides, and a tetranuclear azido/nitrido cluster (Scheme b–f). The only other polynuclear actinide azide complexes are an anionic dinuclear thorium complex (Scheme g) and a neptunium dimer doubly bridged with end‐to‐end azides (Scheme h).…”