55290-33-0Relevant academic research and scientific papers
The use of perchlorato(tetraphenylporphinato)manganese(III) as a reagent for the spectrophotometric determination of anions in nonaqueous solvents
Hinman, A. Scott,McGarty, Karen,Tang, Clement,Pavelich, Brad J.
, p. 545 - 550 (2007/10/02)
Perchlorato(tetraphenylporphinato)manganese(III) (TPPMnClO4) is shown to be a useful reagent for the determination of a variety of anions in nonaqueous media.The analysis is based on the displacement of coordinated perchlorate by more strongly coordinating anions as monitored spectrophotometrically.The procedure is demonstrated for the determination of tetra-alkylammonium salts of nitrate, nitrite, chloride, bromide, iodide, acetate, trifluoroacetate, cyanate, and thiocyanate in acetonitrile.Relative precisions and accuracies of the order of five parts per thousand are indicated.Key words: perchlorato(tetraphenylporphinato)manganese(III), spectrophotometric determination of anions, anions in nonaqueous media.
Study of (Tetraphenylporphinato)manganese(III)-Catalyzed Epoxidation and Demethylation Using p-Cyano-N,N-dimethylaniline N-Oxide as Oxygen Donor in a Homogeneous System. Kinetics, Radiochemical Ligation Studies, and Reaction Mechanism for a Model of Cytochrome P-450
Powell, Michael F.,Pai, Emil F.,Bruice, Thomas C.
, p. 3277 - 3285 (2007/10/02)
Oxygen transfer from p-cyanodimethylaniline (p-CNDMANO) to cyclohexene as well as "intramolecular" oxygen transfer accompained by demethylation to yield p-cyanomonomethylaniline (p-CNMMA) are strongly catalyzed by ligated (tetraphenylporphinato)MnIII (i.e., XMnIIITPP).These reactions have been studied in dry, oxygen-free benzonitrile.Radiochemical studies show that H2O (or TOH) is not bound to XMnIIITPP in aprotic solvents so that the MnIII moiety is pentacoordinate.Oxygen transfer occurs through the reversible formation of the hexacoordinated species p-CNDMANO*MnIII(X)TPP.This species decomposes to p-cyanodimethylaniline (p-CNDMA) + O=MnV(X)TPP.Reactions of cyclohexene with O=MnV(X)TPP yields cyclohexene epoxide and XMnIIITPP whereas p-CNMMA is formed directly from the p-CNDMANO*MnIII(X)TPP complex.The rates of product formation are shown to be dependent upon the nature of the ligand (X- = F-, Cl-, Br-, I-, OCN-).In the absence of the axial ligand X-, the rates of reaction are extremely slow.Thus, the MnIII C2-cap-porphyrin (XMnIIICAPTPP), which can only form an O=MnV porphyrin species wherein the Mn moiety is not complexed to X- as a sixth ligand, shows almost no tendency to act as a catalyst for oxygen transfer.The necessary presence of the axial ligand X- and the dependence of rate upon X- requires the structure of the oxygen transfer species to be quivalent to O=MnV(X)TPP.A kinetic analysis is presented (Scheme III) which has allowed the determination of the influence of the ligands X- upon the various rate constants (Table IV) involved in the overall oxidations.By employing p-CNDMANO as oxygen donor, multiple catalytic turnovers without loss of porphyrin have been realized.
