Actinide phosphido complexes have been shown to undergo interesting and unexpected small molecule activation reactions with C1 compounds such as CO, CO2 and nitriles/isocyanides. However, the overall number of reported reactions is relatively low, and the reactivity of the amido analogs by comparison is even less developed. The reactivity of An-E bonds with small molecules is vital to the assessment of their potential in applications such as organoactinide catalysts, while examining actinide-ligand bonding can probe covalency, which can lead to the design of advanced separations methods. This presentation will examine the reactivity of isostructural actinide-amido and phosphido- complexes of the form (C5Me5)Th(E(H)Mes)2 (E = N, P; Mes = 2,4,6-trimethylphenyl), with small molecules like CO, CO2, phenyl isocyanate and acetonitrile. The reaction of CO with each complex produces starkly different complexes, both of which involve proton migration. The complexes undergo simple insertion reactions with CO2 and phenyl isocyanate, but divergent reactivity occurs with acetonitrile, leading to C-C bond formation and ligand rearrangement.

Comparative insertion reactivity of small molecules into thorium-nitrogen and thorium-phosphorus bonds

2019 Fall National Meeting

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