Photochemical
Route to Actinide-Transition Metal Bonds:
Synthesis, Characterization and Reactivity of a Series of Thorium
and Uranium Heterobimetallic Complexes
Ashleigh
L. Ward
Wayne W. Lukens
Connie C. Lu
John Arnold
10.1021/ja413192m.s002
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
A series of actinide–transition
metal heterobimetallics
has been prepared, featuring thorium, uranium, and cobalt. Complexes
incorporating the binucleating ligand N[<i>ο</i>-(NHCH<sub>2</sub>P<sup>i</sup>Pr<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>]<sub>3</sub> with either Th(IV) (<b>4</b>) or U(IV) (<b>5</b>) and a carbonyl bridged [Co(CO)<sub>4</sub>]<sup>−</sup> unit
were synthesized from the corresponding actinide chlorides (Th: <b>2</b>; U: <b>3</b>) and Na[Co(CO)<sub>4</sub>]. Irradiation
of the resulting isocarbonyls with ultraviolet light resulted in the
formation of new species containing actinide–metal bonds in
good yields (Th: <b>6</b>; U: <b>7</b>); 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 N<sub>4</sub>P<sub>3</sub> 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 <sup>1</sup>H, <sup>1</sup>H–<sup>1</sup>H COSY, <sup>31</sup>P, and variable-temperature
NMR spectroscopy. IR, UV–vis/NIR, and variable-temperature
magnetic susceptibility measurements are also reported.
2014-03-05 00:00:00
actinide chlorides
phosphine arm
thorium complexes
NMR
bond
carbonyl bridged
formation
UV
photolysis method
N 4P ligand
1 H
Characterization
Uranium Heterobimetallic ComplexesA series
uranium complexes
Th
31 P
cobalt center
susceptibility measurements
IR
COSY
Photochemical Route