Part I. Synthesis and properties of electron-deficient porphyrins. Part II. Synthesis of multidentate ligands

5,10,15,20-tetrakis(trifluoromethyl)porphyrin was successfully synthesized in good yield. UV-visible spectroscopic studies indicated that 5,10,15,20-tetrakis(trifluoromethyl)-porphyrin is a highly electron deficient porphyrin. Crystal structure analysis showed that 5,10,15,20-tetrakis(trifluoromethyl)porphyrin has a ruffled core.; beta-Substituted 5,10,15,20-tetrakis(trifluoromethyl)porphyrins were synthesized by regioselective bromination of 5,10,15,20-tetrakis(trifluoromethyl)porphyrinato zinc(II) followed by Suzuki cross coupling of the free-base bromoporphyrins. 2,3-Dibromination was proposed to occur via an addition reaction to the porphyrin beta-pyrrolic bond followed by subsequent oxidation. Theoretical calculation of the charge density of 2-bromo-5,10,15,20-tetrakis(trifluoromethyl)-porphyrinato zinc(II) disfavored that electrophilic aromatic bromination was operating. 2,3,12,13-Tetrabromination was likely formed via the fixation of double bond by electron deficient bromo groups to the antipodal position of the dibromoporphyrin.; 1st (Mn, Fe, Co, Ni, Cu, Zn), 2nd (Rh, Ru, Pd) and 3rd (Re, Ir, Pt) row transition metal complexes of 5,10,15,20-tetrakis(trifluoromethyl)porphyrin were synthesized, of which the structures of the Zn, Pd, Re and Pt metal complexes we determined by X-ray crystallography. The conformation of the porphyrin ring was found to be metal dependent. Novel detrifluoromethylation and ring contraction were found in the metallation of Re and an oxo-rhenium(V) corrolate was characterized.; Fe, Rh and Ru complexes of 5,10,15,20-tetrakis(trifluoromethyl)porphyrin were found to be active catalysts for cyclopropanation of styrene with ethyl diazoacetate. Iodide was a better axial ligand than chloride in Rh(III) porphyrins catalyzed reactions. Ru(por)(CO) showed excellent activities in rate, yield and trans selectivity of the reaction. Electron deficient ruthenium porphyrins exhibited high T.O.F. and T.O.N. CO group was shown to be an essential axial ligand in the catalyst except Ru(tpfpp)(CO). Extremely high activities were found in the Ru(tpfpp)(CO) catalyzed reaction. A reaction mechanism was proposed for Ru(por)(CO) catalyzed cyclopropanation which suggested that a good balance of electron deficiency favored the formation and activity of Ru(por)(CH2CO2Et)(CO) intermediate. A reaction coordinate was also proposed to account for the high diastereoselectivity towards trans-product formation.; Tridentate dipyridyl-para-substituted phenols for the synthesis of bimetallic complexes were successfully synthesized in moderate yield by Stille coupling reaction with 2,6-dibromophenois and 2-tributylstannylpyridines. An improved pentadentate ligand of O,N,O,N,O type containing two phenols, two pyridines and one hydroxy group was also successfully synthesized. (Abstract shortened by UMI.)...