Photochemical Route to Actinide-Transition Metal Bonds: Synthesis, Characterization and Reactivity of a Series of Thorium and Uranium Heterobimetallic Complexes

A series of actinide-transition metal heterobimetallics has been prepared, featuring thorium, uranium, and cobalt. Complexes incorporating the binucleating ligand N[o-((NHCH2PPr2)-Pr-i)C6H4](3) with either Th(IV) (4) or U(IV) (5) and a carbonyl bridged [Co(CO)(4)](-) unit were synthesized from the corresponding actinide chlorides (Th: 2; U: 3) and Na[Co(CO)(4)]. Irradiation of the resulting isocarbonyls with ultraviolet light resulted in the formation of new species containing actinide-metal bonds in good yields (Th: 6; U: 7); this photolysis method provides a new approach to a relatively unusual class of complexes. Characterization by single-crystal X-ray diffraction revealed that elimination of the bridging carbonyl and formation of the metal-metal bond is accompanied by coordination of a phosphine arm from the N4P3 ligand to the cobalt center. Additionally, actinide-cobalt bonds of 3.0771(5) angstrom and 3.0319(7) angstrom for the thorium and uranium complexes, respectively, were observed. The solution-state behavior of the thorium complexes was evaluated using H-1, H-1-H-1 COSY, (31)p, and variable-temperature NMR spectroscopy. IR, UV-vis/NIR, and variable-temperature magnetic susceptibility measurements are also reported.