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Title: 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[-(NHCH2PiPr2)C6H4]3 and Th(IV) (4) or U(IV) (5) with 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 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 rare class of complexes. Characterization by single-crystal X-ray diffraction revealed that elimination of the bridging carbonyl is accompanied by coordination of a phosphine arm from the N4P3 ligand to the cobalt center. Additionally, actinide-cobalt bonds of 3.0771(5) and 3.0319(7) 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.
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Publication Date:
OSTI Identifier:
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Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society
Research Org:
Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, CA (US)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY uranium, cobalt, actinide-metal bond, bonding