Thorium and uranium porphyrins. Synthesis and crystal structure of bis(acetylacetonato)(2,3,7,8,12,13,17,18-octaethylporphyrinato)thorium(IV)

The action of thorium tetrachloride or uranium tetrachloride with porphyrins affords the dichloro complexes (Por)MCl/sub 2/ (M = Th or U). The latter derivatives react with sodium acetylacetonate giving rise to bis(acetylacetonato) complexes (Por)M(acac)/sub 2/. 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-ray diffraction methods: (OEP)Th(acac)/sub 2/, C/sub 46/H/sub 58/N/sub 4/O/sub 4/Th; M/sub r/ = 963; triclinic, P anti 1; a = 9.493 (7), b = 21.185 (5), c = 24.331 (7) A; ..cap alpha.. = 104.18 (2), ..beta.. = 96.11 (4), ..gamma.. = 92.35 (4)/sup 0/; V = 4705 A/sup 3/; d/sub calcd/ = 1.359 g cm/sup -3/; Z = 4; T = 298 K. A total of 9019 intensities were measured on a CAD 4 Enraf-Nonius diffractometer in the omega-2 theta scan mode with monochromatized Mo K..cap alpha.. radiation (1.5 < theta < 20/sup 0/). The crystal structure was refined to a conventional R(F) = 0.047 for 5323 reflections having sigma (I)/I < 0.33. The thorium atom is octacoordinated by the four porphyrin nitrogen atoms and by the four oxygen atoms of the two acetylacetonato groups. 18 references, 2 figures, 8 tables.