Treatment of ThCl 4 with (i) 2/n[K(LL′) n ] in Et 2 O or (ii) 2/m[K(LL) m ] in THF yielded (i) the crystalline, polymeric, heterobimetallic bis(1-aza-allyl)dichlorothorium(IV)-KCl complex [{Th(L⎴L')2(μ3-Cl)(μ-Cl)2K(OEt2)}∞] 1, or (ii) the crystalline, mononuclear bis(β-diketiminato)thorium(IV) chloride [Th(L⎴L)2Cl2] 2 [LL′ = N(SiMe 3 )C(Bu t )C(H)SiMe 3 , LL = N(SiMe 3 )C(Ph) 2 CH]. THF = OC 4 H 8 ]. Details of the NMR spectra of 1 (in C 5 D 5 N) and 2 (in [ 2 H 8 ]toluene), and results of single crystal X-ray diffraction data for both 1 and 2 are presented. While complex 1 was resistant to reduction by K/Na alloy in THF, 2 afforded an unidentified paramagnetic Th(III) complex, g av 2.003 at 300K in PhMe.