ja413192m_si_002.cif (237.6 kB)
Photochemical Route to Actinide-Transition Metal Bonds: Synthesis, Characterization and Reactivity of a Series of Thorium and Uranium Heterobimetallic Complexes
dataset
posted on 2014-03-05, 00:00 authored by Ashleigh
L. Ward, Wayne W. Lukens, Connie C. Lu, John ArnoldA 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.