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Atomically precise copper nanoclusters (NCs) are of immense interest for a variety of applications, but have remained elusive. Herein we report the isolation of a copper NC, [Cu 25 H 22 (PPh 3 ) 12 ]Cl (1), from the reaction of Cu(OAc) and CuCl with Ph 2 SiH 2 , in the presence of PPh 3 . Complex 1 has been fully characterized, including analysis by X-ray crystallography, XANES, and XPS. In the solid state, complex 1 is constructed around a Cu 13 centered-icosahedron and formally features partial Cu(0) character. XANES of 1 reveals a Cu K-edge at 8979.6 eV, intermediate between the edge energies of Cu (0) and Cu(I), confirming our oxidation state assignment. This assignment is further corroborated by determination of the Auger parameter for 1, which also falls between those recorded for Cu(0) and Cu(I).

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Here we describe the synthesis of two imido analogs of the uranyl ion, UO 2+ 2 , in which the oxygens are replaced by divalent alkyl or aryl nitrogen groups: U(N t Bu) 2 I 2 (THF) 2 (1) and U(NPh) 2 I 2 (THF) 3 (2) (where t Bu is tert -butyl and THF is tetrahydrofuran). Both compounds have been fully characterized by standard analytical techniques, including x-ray crystallography, and the chemical bonding between the metal center and the nitrogen ligands was quantified by using hybrid density functional theory calculations. As expected for a uranyl analog, these complexes exhibit linear N-U-N linkages and very short U-N bonds. In addition, the theoretical calculations show strong involvement of the 5f and 6d electrons in the U-N bonding.

In the last few years, considerable progress has been made in the synthesis and characterization of complexes containing actinide-ligand multiple bonds, especially in regards to isolation of terminal oxo, nitrido and carbene-containing complexes. This review summarizes the synthesis, structure, and reactivity of these complexes, from 2010 until present. These complexes are of interest for a variety of reasons, including their potential use in novel catalytic transformations and their ability to engage the 5f orbitals in metal-ligand bonding. Of particular note are the recent syntheses of the first isolable complex containing the nitride-substituted uranyl ion, [NUO](+), and the first report of an isolable terminal uranium nitride. Considerable progress has also been made toward the syntheses of actinide carbenes and thorium complexes containing metal-ligand multiple bonds.