The field of amine borane dehydrogenation has received exhaustive attention, with numerous main group, transition metal and lanthanide metal compounds that serve as catalysts. Interestingly, reactions with the actinides have been ignored. We have discovered that the simple organoactinide compounds, (C5Me5)2AnMe2 (An = Th, U) are pre-catalysts for the dehydrogenation of amine boranes (R2NHBH3 (R = Me; R = H)). Reactions with (C5Me5)2AnMe2 and Me2NHBH3 rapidly affords H2 gas, [Me2NBH2]2, and small quantities of Me2N=BH2 at room temperature with turnover numbers (TONs) and turnover frequencies (TOFs) of ~500 and ~400, respectively. By these metrics, (C5Me5)2AnMe2 are among the fastest catalysts reported for this reaction. In contrast, the corresponding chemistry between (C5Me5)2AnMe2 and NH3BH3 is slow, and results in the formation of (C5Me5)2An(η1-H3B–NH2)(η2-H3B–NH2). This structural motif is unique among actinides, transition metals and main group chemistry. In this talk, we will discuss the details of this chemistry, including mechanistic insights provided from experiment and theoretical calculations.

Filling the gap: Exploration of organoactinide catalysts with amine boranes reveal highly active catalysts and unique structural motifs

253rd National Meeting (2017)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.