%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