Synthesis of a Uranium(VI)-Carbene: Reductive Formation of Uranyl(V)-Methanides, Oxidative Preparation of a [R2C=U=O]2+ Analogue of the [O=U=O]2+ Uranyl Ion (R = Ph2PNSiMe3), and Comparison of the Nature of UIV=C, UV=C, and UVI=C Double Bonds

We report attempts to prepare uranyl(VI)- and uranium(VI) carbenes utilizing deprotonation and oxidation strategies. Treatment of the uranyl(VI)-methanide complex [(BIPMH)UO2Cl(THF)] [1, BIPMH = HC(PPh2NSiMe3)(2)] with benzyl-sodium did not afford a uranyl(VI)-carbene via deprotonation. Instead, one-electron reduction and isolation of di- and trinuclear [UO2(BIPMH)(mu-Cl)UO(mu-O){BIPMH}] (2) and [UO(mu-O)(BIPMH)(mu(3)-Cl){UO(mu-O)(BIPMH)}(2)] (3), respectively, with concomitant elimination of dibenzyl, was observed. Complexes 2 and 3 represent the first examples of organometallic uranyl(V), and 3 is notable for exhibiting rare cation-cation interactions between uranyl(VI) and uranyl(V) groups. In contrast, two-electron oxidation of the uranium(IV)-carbene [(BIPM)UCl3Li(THF)(2)] (4) by 4-morpholine N-oxide afforded the first uranium(VI)-carbene [(BIPM)UOCl2] (6). Complex 6 exhibits a trans-CUO linkage that represents a [R2C=U=O](2+) analogue of the uranyl ion. Notably, treatment of 4 with other oxidants such as Me3NO, C5H5NO, and TEMPO afforded 1 as the only isolable product. Computational studies of 4, the uranium(V)-carbene [(BIPM)UCl2I] (5), and 6 reveal polarized covalent U=C double bonds in each case whose nature is significantly affected by the oxidation state of uranium. Natural Bond Order analyses indicate that upon oxidation from uranium(IV) to (V) to (VI) the uranium contribution to the U=C sigma-bond can increase from ca. 18 to 32% and within this component the orbital composition is dominated by 5f character. For the corresponding U=C pi-components, the uranium contribution increases from ca. 18 to 26% but then decreases to ca. 24% and is again dominated by 5f contributions. The calculations suggest that as a function of increasing oxidation state of uranium the radial contraction of the valence 5f and 6d orbitals of uranium may outweigh the increased polarizing power of uranium in 6 compared to 5.