Reactions of the 2,2,6,6-tetramethylpiperidin-1-oxyl radical (TEMPO) with thorium metallocenes have been examined to define both the radical reaction patterns for organothorium complexes and the coordination chemistry of thorium with TEMPO.  Reactions of TEMPO with methyl, allyl, hydrido, and halo thorium metallocenes, (C5Me5)2ThMe2, (C5Me5)2Th(allyl)2, [(C5Me5)2ThH2]2, and (C5Me5)2ThBr2, respectively, will be described.  Products of composition (C5Me5)2ThR(?1-TEMPO) (R = Me, allyl), (C5Me5)2Th(?1-TEMPO)2, (?2-TEMPO)2ThBr2, and Th(?1-TEMPO)2(?2-TEMPO)2 have been isolated and crystallographically characterized showing that the (TEMPO)1- anion can coordinate ?1 through oxygen and ?2 through oxygen and nitrogen. The reaction of the Th3+ complex (C5Me4H)3Th with TEMPO will also be described, as well as the isolation of a TEMPO radical complex of thorium.

Reactivity of organothorium complexes with TEMPO

248th National Meeting (2014)

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