Intrinsic reactivity of [η5-1,3-(Me3Si)2C5H3]2U(η4-C4Ph2) in small molecule activation

Abstract

The uranium metallacyclocumulene, [η⁵-1,3-(Me₃Si)₂C₅H₃]₂U(η⁴-C₄Ph₂) (3) was isolated from the reaction mixture containing [η⁵-1,3-(Me₃Si)₂C₅H₃]₂UCl₂ (1), potassium graphite (KC₈) and 1,4-diphenylbutadiyne (PhCC–CCPh) in good yield. The reactivity of 3 towards various small organic molecules was evaluated. For example, while complex 3 shows no reactivity towards alkynes and 2,2′-bipyridine, it may deliver the [η⁵-1,3-(Me₃Si)₂C₅H₃]₂U(II) fragment in the presence of Ph₂E₂ (E = S, Se) and Ph₃CN₃, or react as a nucleophile in the presence of carbodiimides, isothiocyanates, aldehydes, ketones, and pyridine derivatives, forming five-, seven- or nine-membered heterometallacycles. On the contrary, addition of Ph₂CS to 3 induces CS bond cleavage yielding the dithiolate complex [η⁵-1,3-(Me₃Si)₂C₅H₃]₂U[S₂(C₁₂H₅Ph₅)] (14). In contrast, the closely related, but sterically more encumbered uranium metallacyclocumulene [η⁵-1,2,4-(Me₃Si)₃C₅H₂]₂U(η⁴-C₄Ph₂) (4) features a more limited reactivity which is restricted to mono- and double insertions with small unsaturated organic molecules such as isothiocyanates, ketones and nitriles.