T. Ken Miyamoto

A notice: incorrect formulation in the synthetic method of 2,2′-bis(diphenylphosphino)biphenyl

Abstract The reaction of 2,2′-dilithiobiphenyl with chlorodiphenylphosphine gives a mixture of triphenylphosphine and 5-phenyldibenzophosphole in almost equal quantities. The formation of the latter phosphine was confirmed by X-ray diffraction study of its platinum(II) derivative. The 31P and 13C NMR data also support the formulation of this reaction. All these experimental facts together clearly demonstrate that the previously reported synthetic method of 2,2′-bis(diphenylphosphino)-biphenyl was erroneously formulated.

Synthesis and characterization of tetrakis(2,6-difluorophenyl)porphinato ruthenium(II)(CO)(N-MeIm); oxidation reaction of hydrocarbon catalyzed by the ruthenium porphyrin

Abstract Synthesis, characterization and properties of a new ruthenium porphyrin, tetrakis(2,6-difluorophenyl)porphinato ruthenium(II)(CO)(N-MeIm), Ru2FP(CO)(N-MeIm), are described. The complex catalyzes the oxidation of hydrocarbons by use of t-BuOOH or hypochlorite as oxidant. To styrene and α-methyl- styrene oxidation, Ru2FP(CO)(N-MeIm)-oxidant systems favor the cleavage of the CC double bond over the formation of the epoxide. Cyclooctene epoxidation and cyclohexane hydroxylation are efficiently performed by the use of TBHP oxidant. On the contrary, hypochlorite oxidant demonstrates only a low catalytic ability for cyclooctene and cyclohexene oxidations.

Metal-metal bonds extended over a porphyrin ring: III. Syntheses and spectral studies of new metal—metal bonded indium porphyrin complexes, (TBPP)In—ML and (5FP)In—ML☆

Abstract Two new series of metal—metal bonded indium porphyrin complexes, (TBPP)In—ML and (5FP)In—ML, where TBPP is the dianion of 5,10,15,20-tetrakis (3,5-di-t-butylphenyl)porphyrin and 5FP is the dianion of 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin, ML is Mn(CO)5, Mo(CO)3Cp, and Co(CO)4, have been synthesized in addition to (OEP)In—ML and (TPP)In—ML. These new metal—metal bonded porphyrin complexes have shown higher solubilities to organic solvents or higher photochemical stabilities as compared with (OEP)In—ML and/or (TPP)In—ML. (P)In—Co(CO)4 complexes where P denotes all of these porphyrin ligands have been obtained in almost quantitative yield by the reaction of (P)In—Cl with LiCo3(CO)10. These porphyrin complexes have shown typical UV-vis spectra to the hyper class. Analysis of the absorption spectra has revealed an anomalous character of (5FP)In—ML complexes. 17O and 13C NMR chemical shifts for CO ligands in (P)In—ML complexes have exhibited only small changes with the change of the porphyrin ligand for the same ML. IR data of (P)In—ML complexes in the ν(CO) region have clearly shown higher frequency shifts in inverse proportion to σ-donor ability of these four porphyrin ligands.