Explorations in metalloporphyrin stereochemistry, physical properties and beyond

Abstract

A review of selected portions of our work in the area of porphyrin structure and physical characterization is presented. Topics covered include early work on periodic trends in first row transtion metalloporphyrins, a survey of electronic structure of iron derivatives including spin-state trends, ligand orientation effects and the elucidtion of unusual low-spin states for iron(II). A discussion of the different tlypes of high-spin iron(II) complexes and the effects of hydrogen bonding is given. A survey of nitric oxide (NO) derivatives is presented as well as a brief introduction into the use of nuclear resonance vibrational spectroscopy for the study of iron porphyrins and heme proteins.

Structural investigation of 5,10-A2B2-type porphyrins: palladium(II) and zinc(II) complexes of 5,10-dibromo-15,20-bis(4-methylphenyl)porphyrin

“…The structural chemistry of porphyrins is one of the best investigated areas of coordination chemistry. Many studies are available on metal coordination (Scheidt, 2008), aspects of macrocycle modification (Chmielewski & Latos-Grazynski, 2005), supramolecular chemistry (Beletskaya et al, 2009) and nonplanar systems (Senge, 2006). The latter have been the focus of conformational analyses which highlighted the flexible character of the porphyrin macrocycle, especially in the case of highly substituted systems, i.e.…”

A pair of highly biotolerated diamagnetic and paramagnetic iron(ii) complexes displaying electroneutrality

“…Indeed, electroneutral, low-spin iron(II) complexes that are binary and thus may exhibit high stability in competitive solvents, are a relative rarity. While most porphyrin or phthalocyanine complexes do not apply 7 (they almost always display two fairly labile, monodentate ligands in their apical positions, 9,10 the recently reported clathrochelates (macrobicyclic boron-capped tris-dioximates) are eletroneutral, low-spin iron(II) complexes of impressive stability. 11 However, it is not obvious how to derive a high-spin version thereof.…”

Synthesis and Acid-base Properties of Isomeric Tetrachlorooctabromo- and Tetrabromooctachlorotetraphenylporphyrins

“…m/z (Ie, %): 1439. 9 (4). Thionyl chloride (4 mL) was added to the compound 2 (0.02 g, 0.0203 mmol) in CHCl 3 -DMF mixture (12 mL, 1:1).…”

“…Synthetic porphyrins having a planar or almost planar molecules structure have been thoroughly studied. [1][2][3][4][5] However, according to the data, [6][7][8][9][10][11][12][13] the porphyrin macrocycle is flexible enough and can exist in no planar conformations. The ability of spatially distorted polyhalogensubstituted metalloporphyrins to exhibit catalytic activity in oxidation reactions is of great interest.…”