Organometallic chemistry of the actinides .3. Novel 1-aza-allyl- and beta-diketiminatothorium chlorides; X-ray structures of [{Th(LL')(2)(mu(3)-Cl)(mu-Cl)(2)K(OEt2)}(infinity)] and [Th(LL)(2)Cl-2][LL'=N(SiMe3)C(Bu-t)C(H)SiMe3; LL={N(SiMe3)C(Ph)}(2)CH]

Treatment of ThCl4 with (i) 2/n[{K(LL')}(n)] in Et2O or (ii) 2/m[{K(LL)}(m)] in THF yielded (i) the crystalline, polymeric, heterobimetallic bis(1-aza-allyl)dichlorothorium(IV)-KCl complex [{Th(LL')(2)(mu(3)-Cl)(mu-Cl)(2)K(OEt2)}(x)] 1, or (ii) the crystalline, mononuclear bis(beta-diketiminato)thorium(IV) chloride [Th(LL)(2)Cl-2] 2 [LL'=N(SiMe3)C(Bu-t)C(H)SiMe3, LL = {N(SiMe3)C(Ph)}(2)CH, THF = OC4H8]. Details of the NMR spectra of 1 (in C5D5N) and 2 (in [H-2(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 300 K in PhMe. (C) 1997 Elsevier Science S.A.