STAR PORPHYRAZINES - PERIPHERAL CHELATION OF PORPHYRAZINEOCTATHIOLATEBY DIPHOSPHINONICKEL IONS

We have synthesized new pentametallic macrocyclic complexes based on t he polynucleating ligand, porphyrazine-2,3,7,8,12,13,17,18-octathiolat e, (pzot)8-. This ligand can be thought of as a porphyrazine (tetraaza porphyrin) bearing four dithiolene moieties peripherally at the beta-p yrrole positions, and we show that a transition-metal ion can be chela ted to each of the four peripheral dithiolene moieties. The complexes [(P-P)Ni]4[Ni(pzot)] (2a, P-P = dppe; 2b, P-P = dppy; 2c, P-P = dppb; 2d, P-P = dcpe) have been synthesized and characterized. Complex 2a cr ystallizes in the orthorhombic space group Cmc2(1) (No. 36) with 4 mac rocycles and 16 solvent molecules (N,N-dimethylformamide) in a unit ce ll of dimensions a = 24.630(5) angstrom, b = 20.607(4) angstrom, c = 3 0.675(6) angstrom. The [Ni(pzot)]8- ligand in 2a coordinates four Ni(P -P) moieties around its periphery with the two thiolate sulfur atoms o f each pyrrole binding a nickel ion in a bidentate (S-S) coordination mode. This is in contrast to the reaction of [Ni(pzot)]8- with SnR2X2, which yielded Ni(pzot)(SnR2)4 (1), where each tin is coordinated in t he tridentate (S-N-S) mode, with the thiolate sulfur atoms from two py rroles and one m-nitrogen atom as ligands from the macrocycle (Velazqu ez, C. S.; Fox, G. A.; Broderick, W. E.; Andersen, K; Anderson, O. P.; Barrett, A. G. M.; Hoffman, B. M. J. Am. Chem. Soc. 1992, 114, 7416-7 424). Comparison of the crystal structures of 1,2a, and uo(octakis(met hylthio)porphyrazinato)magnesium(II) (Mg(omtp)), a structurally uncons trained reference compound with eight peripheral methylthio groups, sh ows that [Ni(pzot)]8- adjusts to accommodate either the (S-S) or (S-N- S) modes of coordinating the metal ions at the periphery by a swing of the C(beta)-S bond. H-1 and P-31 NMR studies have been used to determ ine the nature of the coordination of the Ni(P-P) units to the [Ni(pzo t)]8- macrocycle in solution. Model compounds were synthesized as stru ctural references to mimic both possible coordination sites of the [Ni (pzot)]8- ligand. The H-1 and P-31 NMR chemical shifts of macrocycles 2a-d and their respective bidentate model complexes clearly indicate t hat the macrocycle in solution also binds the Ni(P-P) units in a biden tate fashion. The electronic absorption spectra of complexes 2a-d show a red-shift of the absorbance in the Q-band region due to interaction of the porphyrazine pi-system with the four peripheral metal ions.