The action of thorium tetrachloride or uranium tetrachloride with porphyrins affords the dichloro complexes (Por)MC12 (M = Th or U). The latter derivatives react with sodium acetylacetonate giving rise to bis(acety1acetonato) complexes (Por)M(acac)l. The two series of complexes are characterized on the basis of mass spectral, IR, UV-visible, and NMR data. The crystal structure of the title compound has been determined by X-ra diffraction methods: (OEP)Th(acac),, C46Hs8N404Th; M, = 963; triclinic, Pi; a = 9.493 (7), b = 21.185 (5), c = 24.331 (7) i; (Y = 104.18 (2), B = 96.11 (4), y = 92.35 (4)O; V = 4705 A'; d,,, = 1.359 g Z = 4; T = 298 K. A total of 9019 intensities were measured on a CAD 4 Enraf-Nonius diffractometer in the w-20 scan mode with monochromatized Mo Ka radiation (1.5 < 8 < 20'). The crystal structure was refined to a conventional R(F) = 0.047 for 5323 reflections having a(Z)/Z < 0.33. The thorium atom is octacoordinated by the four porphyrin nitrogen atoms and by the four oxygen atoms of the two acetylacetonato groups.
The reaction of dichlorothorium complexes of octaethyl‐ or tetraphenylporphyrin with sodium carbonate in oxygen‐free THF gives the corresponding dihydroxo‐porphyrinatothorium compounds as trimers (80 and 82% yield).
The reaction of the tetrachlorides (I) with the porphyrins (II) affords the dichloro complexes (III) which react with sodium acetylacetonate to give the derivatives (IV).
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