Synthesis and reactivity of palladium biliverdin, reactivity of iron verdoheme, and crystallization of Diels-Alder adducts of carbon(60)

Part 1. Insertion of palladium into octaethylbilindione formed the tetranuclear complex, [Pd₄(OEB)₂] or [Pd(OEB·)] depending upon reaction time and the amount of palladium acetate. [Pd(OEB·)] has spectroscopic features, 1H NMR, EPR, cyclic voltammetry, and UV/Vis spectra similar to known bilindione complexes of copper, cobalt, and nickel. [Pd₄(OEB)₂] displayed unique reactivity stemming from π-coordination between the PdI-PdI bond and the bilindione ligand. Addition of diiodine to a pyridine solution of [Pd₄(OEB)₂] resulted in the rearrangement and oxidation of the ligand. Studies of the oxidation and acid reactivity of these bilindione complexes showed that the rearranged product is remarkably stable.; Titration of aryl Grignard reagents (phenyl or p-tolyl) with bishaloiron(III) verdoheme (Cl or Br) at 298, 282, or 203 K and bromoiron(II)verdoheme at 203 K was followed by 1H NMR spectroscopy. Studies at room temperature detected a series of equilibria between iron (III) and iron (II) complexes including XFIIOEOP, XPhFeIIIOEOP, and ArFe IIEOP (X = Cl or Br). Titration at 203 K resulted in the formation of ClFeIIEOP and ultimately [FeIIOEOP-Ph], which was confirmed by titration with ClFeIIOEOP. Oxidation of [FeOEOP-Ph] formed X₂FeIIIOEOP and (X)(Ar)FeIIIOEOP.; Part 2. Careful control of solvent ratios was important for the growth of x-ray quality crystals of C₆₀ pentacene, bisfullerene [C₆₀] diphenylpentacene and the product resulting from amination and hydrogenation of the adduct 4,5-dihydro-3,6-di(2′-pyridyl)pyridazine of C₆₀. C₆₀ pentacene was s a well-ordered structure which packs such that the pentacene appendages appears to support the next fullerene. Bisfullerene [C₆₀] diphenylpentacene contained a well-ordered fullerene but a complex disorder in the solvent molecules. The product resulting from amination and hydrogenation of the adduct 4,5-dihydro-3,6-di(2 ′-pyridyl)pyridazine of C₆₀ contained a mixture of both diastereomers. The major diastereomer had a refined population of 0.529(3). The C₆₀ of the diastereomers superimposed such that the position of the 5- and 6-membered rings at the site where the adduct adds was reversed. Co-crystallization of C₆₀ and C₇₀ with CIInOEP, ZnOEP-meso NO₂, CoOEP meso NO₂ and CIInOEP-meso NO₂ resulted in structures of C₆₀·CIInOEP·CHCl₃ , C₇₀·CIIn(OEP) CHCl₃, C₇₀·Zn(OEP-NO ₂)·solvent, and C₇₀·Co(OEP-NO₂)·solvent containing disordered fullerenes in all cases and disordered solvents in the cases of co-crystallization of the nitro porphyrins. Modeling of the fullerene was complicated due to fullerenes which superimposed differently in the various structures.