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• 77370-96-8 cis-di(chloro)(tetraphenylporphyrinato^(2-))zirconium(IV) 
• 124-38-9 carbon dioxide 
• 108-95-2 phenol 

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Phthalocyaninates and tetraphenylporphyrinates of high co-ordinated ZrIV/HfIV with hydroxo, chloro, (di)phenolato, (hydrogen)carbonato, and (amino)carboxylato ligands

Crystals of tetra(n-butyl)ammonium cis-tri(phenolato)phthalocyaninato(2-)zirconate(IV) (2) and -hafnate(IV) (1), di(tetra(n-butyl)ammonium) cis-di(tetrachlorocatecholato(O, O′)-phthalocyaninato(2-)zirconate(IV) (3), and cis-(di(μ-alaninato(O,O′)di(μ-hydroxo))di(phthalocyaninato(2-) zirconium(IV)) (12) have been isolated from tetra(n-butyl)ammonium hydroxide solutions of cis-di(chloro)phthalocyaninato(2-)zirconium(IV) and -haf-nium(IV), respectively, and the corresponding acid in polar organic solvents. Similarly, with cis-di(chloro)tetraphenylporphyrinato(2-)-zirconium(IV), cis[Zr(Cl)2tpp] as precursor crystalline tetra(n-bu tyl)ammonium cis-tetrachlorocatecholato(O,O′)hydrogentetra chlorocatecholato(O)tetraphenylporphyrinato(2-)zirconate(IV) (4), cis-hydrogencarbonato(O,O′)phenolatotetraphenylporphyrinato-(2-) zirconium(IV) (6), cis-di(benzoato(O,O′))tetraphenylporphyrinato(2-)zirconium(IV) (11), and cis-tetra(μ-hydroxo)di(tetraphenyl-porphyrinato(2-)zirconium(IV)) (13) with a cis-arrangement of the symmetry equivalent μ-hydroxo ligands, and from di(acetato)tetraphenylporphyrinato(2-)zirconium(IV) the corresponding trans-isomer (14) have been prepared. The endothermic dehydration at 215°C of 13/14 yields μ-oxodi(μ-hydroxo)di(tetraphenylporphyrinato(2-)zirconium(IV)) (15). 15 also precipitates on dilution of a solution of cis[Zr(X)2tpp] (X = Cl, OAc) in dmf/(nBu4N)OH with water, while on prolonged standing of this solution on air tri(tetra(n-butyl)ammonium) cis-(nido〈di(carbonato(O,O′)) undecaaquamethoxide〉tetraphenylporphyrinato(2-)zirconate(IV) (7) crystallizes, in which ZrIV coordinates a supramolecular nestlike nido〈(O2CO)2(H2O) 11OCH3〉5- cluster anion stabilised by hydrogen bonding in a nanocage of surrounding (nBu4N)+ cations. On the other hand, cis[Zr(Cl)2pc] forms with (Et4N)2CO3 in dichloromethane di(tetraethylammonium) cis-di(carbonato(O,O′)phthalocyaninato(2-)zirconate(IV) (5). cis[Zr(Cl)2tpp] dissolves in various O-donor solvents, from which cis-di(chloro)dimethylformamidetetraphenylporphyrinato(2-)zirconium(IV) (8), cis-di(chloro)dimethylsulfoxidetetraphenylporphyrinato(2-)zirconium(IV) (9), and a 1:1 mixture (10) of cis-di(chloro)dimethylsulfoxidetetraphenylporphyrinato(2-)zirconium(IV) (10a) and cis-chlorodi(dimethylsulfoxide)tetraphenylporphyrinato(2-)zirconium(IV) chloride (10b) crystallize. All complexes contain solvate molecules in the solid state, except 3. ZrIV/HfIV is directed by ～1 A out of the plane of the tetrapyrrolic ligand (pc, tpp) towards the mutually cis-coordinated axial ligands. In the more concavely distorted phthalocyaninates, ZrIV is mainly eight-coordinated and in the tetraphenylporphyrinates seven-coordinated. The octa-coordinated Zr atom is in a distorted quadratic antiprism, and the hepta-coordinated one is in a square-base-trigonal-cap cooordination polyhedron. In most tpp complexes, the Zr atom is displaced by up to 0.3 A out of the centre of the coordination polyhedron towards the tetrapyrrolic ligand. In 13/14, both antiprisms are face shared by an O4 plane, and in 12 they are shared by an O2 edge and the O atoms of the bridging aminocarboxylates, the dihedral angle between the O4 planes of both antiprisms being 50.1(1)°. The mean Zr-Np distance is 0.05 A longer in the pc complexes than in the tpp complexes (d(Zr-Np)pc = 2.31 A). In the monophenolato complexes, the mean Zr-O distance (～2.00 A) is shorter than in the complexes with other O-donor ligands (d(Zr-O)pc = 2.18 A; d(Zr-O)tpp = 2.21 A); the Zr-Cl distances vary between 2.473(1) and 2.559(2) A (d(Zr-Cl)tpp = 2.51 A). d(C-Oexo) = 1.494(4) A in the bidentate hydrogencarbonato ligand in 6 is 0.26 A longer than in the bidentate carbonato ligands in 5 and 7.9 and 10a are rotamers slightly differing by the orientation of the axial ligands with respect to the tpp ligand. In 1-4, 6, and 11 the phenolato, catecholato, and benzoato ligands, respectively, are in syn- and/or anti-conformations with respect to the plane of the macrocycle. π-Dimers with modest overlap of the neighbouring macrocyclic tings are observed in 5, 6, 8, 9, 10b, 12, and 14. The common UV/Vis spectroscopical and vibrational properties of the new phthalocyaninates and tetraphenylporphyrinates scarcely reflect their rich structural diversity.