A classification of kinetics of metalloporphyrin formation is presented according to the composition of the activated complex involved in the reaction. In the reaction of large metal ions, such as mercury(II) and cadmium(II) with porphyrins, these metal ions can not fit into the porphyrin nucleus and they are out—of-plane in the metalloporphyrin. In this case the reaction is relatively fast and...

Manganese porphyrin-linker-triple-helix-forming oligonucleotide molecules were prepared and their ability to cleave in vitro a double-stranded DNA target present in the HIV-1 genome was studied. The nature of the linker is a determining factor of the cleavage efficiency. Cleavage yields as high as 80% were observed when the linker was a spermine residue and in the absence of a large excess of f...

Effects of imidazoles and substituted pyridines and pure s-donors on the oxidation of cyclooctene with NaIO4 by 5,10,15,20-tetraphenylporphyrinato-manganese(III) acetate, Mn(TPP)OAc, and 5,10,15,20-Tetramesitylporphyrinato-manganese(III) acetate, Mn(TMP)OAc, catalysts in CH2Cl2-H2O solvent are studied. Coordination of the nitrogen donors to the Mn...

Three five-coordinate, high spin manganese(ii) "picket fence" porphyrin complexes, [Mn(TpivPP)(L)] (TpivPP = α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrinato; L = 1-MeIm (1-methylimidazole), 1-EtIm (1-ethylimidazole) and 2-MeHIm (2-methylimidazole)), are synthesized and studied by single-crystal X-ray, UV-vis and electronic paramagnetic resonance (EPR) spectroscopy. Structural parameters are in...

The structural and reactive properties of the acetyl-protected "one-legged" manganese porphyrin [SAc]P-Mn(III)Cl on Ag(100) have been studied by NEXAFS, synchrotron XPS and STM. Spontaneous surface-mediated deprotection occurs at 300 K accompanied by spreading of the resulting thio-tethered porphyrin across the metal surface. Loss of the axial chlorine ligand occurs at 498 K, without any demeta...

New sulfate and hydrogen sulfate complexes of metalloporphyrins have been synthesized and crystallographically characterized and their photochemistry examined. Irradiation of [Mn(TPP)],(SO,) and Mn(TPP)(OS03H) (where TPP = 5,10,15,20-tetraphenylporphyrinate(2-)) produces Mn"(TPP) quantitatively, with quantum yields of 7.1 X IO4 and 9.8 X IO-', respectively. In contrast to other manganese oxoani...