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A new synthesis of Th(II) complexes has been identified involving addition of simple MX salts (M = Li, Na, K; X = H, Cl, Me, N3) to Cp′′3ThIII [Cp′′ = [C5H3(SiMe3)2] in the presence of 18-crown-6 or 2.2.2-cryptand, forming [M(chelate)][Cp′′3ThII] and Cp′′3ThIVX. Cptet3ThIII (Cptet = C5Me4H) reacts with KH to form Cptet3ThIVH and the C–H bond activation product, [K(crypt)]{[Cptet2ThIVH[η15-C5Me3H(CH2)]}.

Graphical abstract: Anion-induced disproportionation of Th(iii) complexes to form Th(ii) and Th(iv) products

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