Metal–Metal Bonding in Uranium–Group 10 Complexes

[Image: see text] Heterobimetallic complexes containing short uranium–group 10 metal bonds have been prepared from monometallic IU(IV)(OAr(P)-κ(2)O,P)(3) (2) {[Ar(P)O](−) = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U–M bond in IU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)(3)M(0), M = Ni (3–Ni), Pd (3–Pd), and Pt (3–Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3–Ni with two further U–Ni complexes XU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)(3)Ni(0), X = Me(3)SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U–M bonds are significantly shorter than any other crystallographically characterized d–f-block bimetallic, even though the ligand flexes to allow a variable U–M separation. Excellent agreement is found between the experimental and computed structures for 3–Ni and 3–Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U–M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U–Ni bond than U–Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U–X adducts 3–Ni, 4, and 5. The data show a trend in uranium–metal bond strength that decreases from 3–Ni down to 3–Pt and suggest that exchanging the iodide for a fluoride strengthens the metal–metal bond. Despite short U–TM (transition metal) distances, four other computational approaches also suggest low U–TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3–Pd than 3–Ni, consistent with slightly larger U–TM bond orders in the latter. Computational studies of the model systems (PH(3))(3)MU(OH)(3)I (M = Ni, Pd) reveal longer and weaker unsupported U–TM bonds vs 3.