Synthesis and Characterization of Chelating Alkyl-borohydride Complexes of Thorium and Uranium: Th(CH2NMe2BH3)4 and U(CH2NMe2BH3)4

R. Joseph Lastowski, Christopher M. Caroff, Konstantinos D. Vogiatzis, Gregory S. Girolami

Research output: Contribution to journalArticlepeer-review

Abstract

This paper describes the synthesis and characterization of two actinide alkyls: thorium and uranium compounds of stoichiometry M(CH2NMe2BH3)4 (M = Th, U) where CH2NMe2BH3- is the boronatodimethylaminomethyl group (abbreviated BDAM). The crystal structures of these compounds show that the coordination geometry of the metal center can be described in terms of a D2d dodecahedron, whose eight vertices are defined by the four metal-bound carbon atoms and the four boron atoms of the BH3 groups. Two of the BH3 groups in each compound bind to the metal centers in a κ2 fashion (i.e., by means of two B-H-M bridges) and two in a κ1 fashion. Thus, both compounds can also be described as ten-coordinate in which four carbon atoms and six hydrogen atoms form the inner coordination sphere. The structures of both complexes and the nature of the BH3-M interactions were investigated computationally. The NMR spectra of the diamagnetic thorium(IV) compound and paramagnetic uranium(IV) compound are discussed; both compounds are fluxional in solution even at −124 °C. Variable temperature magnetization studies of the paramagnetic uranium(IV) compound in the solid state are consistent with its tetravalent oxidation state.

Original languageEnglish (US)
Pages (from-to)2839-2848
Number of pages10
JournalOrganometallics
Volume42
Issue number19
DOIs
StatePublished - Oct 9 2023

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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