In contrast to molecular uranium redox chemistry, which has blossomed in recent years due to the relatively facile interchange between a variety of oxidation states, the corresponding thorium chemistry is underdeveloped as the +4 oxidation state predominates and strong reducing agents are often necessary to access subvalent compounds. Inspired by the remarkable small molecule activation properties of U(III) compounds, we have embarked upon full reactivity studies of Lappert's Th(III) complex [Th{C5H3(SiMe3)2-1,3}3] (1) and its hydrocarbyl analogue, [Th(C5H3tBu2-1,3)3] (2). For 1, we are discovering reactivity profiles that complement and contrast with better understood homoleptic U(III) substituted cyclopentadienyl complexes. For 2, we have employed pulsed EPR spectroscopy to determine spin density at ligand C5 ring 13C nuclei, and therefore the covalency of Th-C bonds in this molecule. Our recent progress will be discussed here.

Thorium redox chemistry and a new way to measure actinide covalency by pulsed EPR spectroscopy

253rd National Meeting (2017)

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