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

1.超结构卟啉和氧化反应的合成，一种新的bulky卟啉，中四rakis（2-methoxy-5， 5， 8，8-四甲基-6，6， 7，7-四氢-1-anthryl）卟啉（abbr）。P）是合成的。四种过敏原（alphabetaalphabeta，alphaalphabeta，alphaalphaalphabeta，alphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalphaalpha）被色谱法分离和纯化，由色谱法。所有的异构体都展示了非凡的高热稳定性，朝着异源化。在高温下（c.）190^OC）在2-（2-甲氧基）乙醇，钌（II）离子被添加到每个异构体的残留中。用^1H-核磁共振光谱分析分析了异体钌（II）的卟啉（Py或CO），另一种钌卟啉（2，6-二氟苯基）卟啉（II） （CO） （N-Melm）。它被催化氧化氢碳（苯乙烯、α-甲基苯乙烯、环氯烯或环氯酮），是通过t-BuOOH或hypochlorite作为氧化物的用途。抗塑性铂复合体的合成和结构. A1 R，2 R-二氨基环氯铂（II）复合体的B_2O_5H_2^&lt;2-&gt;， （<14>C_6H_N_2）Pt（B_2O_5H_2）·H_2O，通过反应合成（C_6H_N_2<14>）Pt（OH）_2与二聚氰胺四氢酸存在于各种溶液中。揭示了B_2O_5H_2^&lt;2-&gt;阴离子和铂（II）切割的X射线结构分析。新的核铂（II）复合体系列， [PtL_2（slac）]_2·H_2O在slac =硫酸盐dianion中; L_2 = 1，2-二氨基环己酮（1a-1c）或1，2-二氨基乙烷（2）， L = isopropylamine （3）或ammine （4），已从[PtL_2（OH）_2]的反应中制备。他们在晶体中有二-mu-carboxylato桥接了二核二离子结构。在它们中间，复合体（1a-1c）显示对老鼠白血病L1210的有意义的拮抗剂或活动。

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.