%0 Generic %A Ward, Ashleigh L. %A Lukens, Wayne W. %A Lu, Connie C. %A Arnold, John %D 2014 %T Photochemical Route to Actinide-Transition Metal Bonds: Synthesis, Characterization and Reactivity of a Series of Thorium and Uranium Heterobimetallic Complexes %U https://acs.figshare.com/articles/dataset/Photochemical_Route_to_Actinide_Transition_Metal_Bonds_Synthesis_Characterization_and_Reactivity_of_a_Series_of_Thorium_and_Uranium_Heterobimetallic_Complexes/2318227 %R 10.1021/ja413192m.s002 %2 https://acs.figshare.com/ndownloader/files/3955864 %K actinide chlorides %K phosphine arm %K thorium complexes %K NMR %K bond %K carbonyl bridged %K formation %K UV %K photolysis method %K N 4P ligand %K 1 H %K Characterization %K Uranium Heterobimetallic ComplexesA series %K uranium complexes %K Th %K 31 P %K cobalt center %K susceptibility measurements %K IR %K COSY %K Photochemical Route %X A series of actinide–transition metal heterobimetallics has been prepared, featuring thorium, uranium, and cobalt. Complexes incorporating the binucleating ligand N­[ο-(NHCH2PiPr2)­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) Å and 3.0319(7) Å for the thorium and uranium complexes, respectively, were observed. The solution-state behavior of the thorium complexes was evaluated using 1H, 1H–1H COSY, 31P, and variable-temperature NMR spectroscopy. IR, UV–vis/NIR, and variable-temperature magnetic susceptibility measurements are also reported. %I ACS Publications