Exploitation of Superstructure Porphyrin and Other Functional Complexes : Structure-Function Relationship.

1. Syntheses of Superstructure Porphyrin and Oxygenation Reaction.A new bulky Porphyrin，meso-tetrakis (2-methoxy-5, 5,8,8 -tetramethyl- 6,6,7，7- tetrahydro1 -anthryl) porphyrin (abbr. AP) was synthesized. Four atropisomers (alphabetaalphabeta，alphaalphabetabeta, alphaalphaalphabeta,alphaalphaalpha: were separated and purified by column chromatography. The isomers all showedremarkable high thermal stability toward atropisomerization. Under a high temperature （ca. 190）in 2- (2-methoxyethoxy) ethanol，ruthenium (II) ion was incorporated into each isomer with the retention of the ligand conformation.The stereoselectivity of The isomeric ruthenium (II) porphyrins to incoming ligands (py or CO) wasexamined by 1h - nmr spectroscopy.Another ruthenium porphyrintetrakis (2,6-difluorophenyl) porphinato ruthenium (II) （CO）was prepared. It catalyzed oxidation of hydrocarbons (styrene, alpha-methylstyrene，cyclooctene or cyclohexane) use of t-BuOOH or hypochlorite as oxidant.2. Syntheses and Structureof Antineoplastic Platinum Complexes.A 1r，2 r - d iaminocyclohexaneplatinum (ii) complex)》of b _ 2 o 5 h译文:2 ^ < 2 - >,(c 6 h译文:< 14 > 2 n) pt (b _ 2 o 5 h译文:2)·h 2 o,is synthesized by reacting (c_6h_< 14> n_2)Pt(OH)_2 with boric acid in the presence of dipotassiumtetraborate tetrahydrate in aqueous solution X-ray structural analysis revealed that theb_2_5 h_2 <2-> anion and the platinum (II) cation from a x-membered chelate. a series of newdinuclear platinum (II) complexes, [ptl_2 (slac)]_2·h_2 O where slac = sulfoacetate dianion；l_2 = 1,2-diaminocyclohexane (1a-1c) or 1,2-diaminoethane (2)，L = isopropylamine (3) or ammine (4)，have been prepared from the reaction of [ptl_2 (OH)_2] with sulfoacetic acid. They havedi-mu-carboxylato bridged dinuclear zwitterionic structures in crystals. Among them，complexes (1a-1c) show significant antitumor activities against mice leukemia L1210。

1. Syntheses of Superstructure Porphyrin and Oxygenation Reaction.A new bulky porphyrin, meso-tetrakis (2-methoxy-5, 5, 8, 8-tetramethyl-6, 6, 7, 7-tetrahydro-1-anthryl) porphyrin (abbr. AP) was synthesized. Four atropisomers (alphabetaalphabeta, alphaalphabetabeta, alphaalphaalphabeta, alphaalphaalpha) were separated and purified by column chromatography. The isomers all showed remarkable high thermal stability toward atropisomerization. Under a high temperature (ca. 190^OC) in 2- (2-methoxyethoxy) ethanol, ruthenium (II) ion was incorporated into each isomer with the retention of the ligand conformation. The stereoselectivity of the isomeric ruthenium (II) porphyrins to incoming ligands (py or CO) was examined by ^1H-NMR spectroscopy.Another ruthenium porphyrin, tetrakis (2,6-difluorophenyl) porphinato ruthenium (II) (CO) (N-Melm), was prepared. It catalyzed oxidation of hydrocarbons (styrene, alpha-methylstyrene, cyclooctene or cyclohexane) by use of t-BuOOH or hypochlorite as oxidant.2. Syntheses and Structure of Antineoplastic Platinum Complexes.A 1R, 2R-diaminocyclohexaneplatinum (II) complex of B_2O_5H_2^<2->, (C_6H_<14>N_2)Pt(B_2O_5H_2)・H_2O, is synthesized by reacting (C_6H_<14>N_2)Pt(OH)_2 with boric acid in the presence of dipotassium tetraborate tetrahydrate in aqueous solution. X-ray structural analysis revealed that the B_2O_5H_2^<2-> anion and the platinum (II) cation from a six-membered chelate.A series of new dinuclear platinum (II) complexes, [PtL_2(slac)]_2・H_2O where slac = sulfoacetate dianion ; L_2 = 1,2-diaminocyclohexane (1a-1c) or 1,2-diaminoethane (2), L = isopropylamine (3) or ammine (4), have been prepared from the reaction of [PtL_2(OH)_2] with sulfoacetic acid. They have di-mu-carboxylato bridged dinuclear zwitterionic structures in crystals. Among them, complexes (1a-1c) show significant antitumor activities against mice leukemia L1210.