Phthalocyaninates And Tetraphenylporphyrinates Of High Co-Ordinated Zr-Iv/Hf-Iv 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(mu-alaninato-(O,O')di(mu-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 -hafnium(IV), respectively, and the corresponding acid in polar organic solvents. Similarly, with cis-di(chloro)tetraphenylporphyrinato(2-)zirconium(IV), (cis)[Zr(Cl)(2)tpp] as precursor crystalline tetra(n-butyl)ammoniumcis-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(mu-hydroxo)di(tetraphenylporphyrinato(2-)zirconium(IV)) (13) with a cis-arrangement of the symmetry equivalent mu-hydroxo ligands, and from di(acetato)tetraphenylporphyrinato(2-)zirconium(IV) the corresponding trans-isomer (14) have been prepared. The endothermic dehydration at 215degreesC of 13/14 yields mu-oxodi(mu-hydroxo)di(tetraphenylporphyrinato(2-)zirconium(IV)) (15). 15 also precipitates on dHution of a solution of (cis)[Zr(X)(2)tpp] (X = Cl, OAc) in dmf/((Bu4N)-Bu-n)OH with water, while on prolonged standing of this solution on air tri(tetra(n-butyl)anmonium) cis-((nido)(di(carbonato(O,O'))undecaaquamethoxide) tetraphenylporphyrinato(2-)zirconate (IV) (7) crystallizes, in which Zr-IV coordinates a supramolecular nestlike (nido) <(O2CO)(2)(H2O)(11)OCH3>)(5-) cluster anion stabilised by hydrogen bonding in a nanocage of surrounding ((Bu4N)-Bu-n)(+) cations. On the other hand, (cis)[Zr(Cl)(2)pc] forms with (Et4N)(2)CO3 in dichloromethane di(tetraethylammonium) cis-di(carbonato(O,O')phthalocyaninato(2-)zirconate(IV) (5). (cis)[Zr(Cl)(2)tpp] dissolves in various O-donor solvents, from which cis-di(cliloro)dimethylformamidetetraphenylpophyrinato(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- chloro di(dimethylsulfoxide) tetraphenylporphyrinato(2-)zirconium(IV) chloride (10b) crystallize. All complexes contain solvate molecules in the solid state, except 3. Zr-IV/Hf-IV is directed by similar to1 Angstrom out of the plane of the tetrapyrrolic ligand (pc, tpp) towards the mutually cis-coordinated axial ligands. In the more concavely distorted phthalocyaninates, Zr-IV 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 Angstrom out of the centre of the coordination polyhedron towards the tetrapyrrolic ligand. In 13/14, both antiprisms are face shared by an O-4 plane, and in 12 they are shared by an O-2 edge and the O atoms of the bridging aminocarboxylates, the dihedral angle between the O-4 planes of both antiprisms being 50.1(1)degrees, The mean Zr-N-p distance is 0.05 A31 Angstrom). In the monophenolato complexes, the mean Zr-O distance (similar to2.00 Angstrom) is shorter than in the complexes with other O-donor ligands (d(Zr-O)(pc) = 2.18 Angstrom; d(Zr-O)(tpp) = 2.21 Angstrom); the Zr-Cl distances vary between 2.473(1) and 2.559(2) Angstrom (d(Zr-Cl)(tpp) = 2.51 Angstrom). d(C-O-exo) = 1.494(4) Angstrom in the bidentate hydrogencarbonato ligand in 6 is 0.26 Angstrom 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. pi-Dimers with modest overlap of the neighbouring macrocyclic rings 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.