A NOVEL COORDINATION MODE OF TERMINAL GROUP OF SOME TAILED PORPHYRIN IRON（Ⅲ） COMPLEXES

ＡＮＯＶＥＬＣＯＯＲＤＩＮＡＴＩＯＮＭＯＤＥＯＦＴＥＲＭＩＮＡＬＧＲＯＵＰＯＦＳＯＭＥＴＡＩＬＥＤＰＯＲＰＨＹＲＩＮＩＲＯＮ（Ⅲ）ＣＯＭＰＬＥＸＥＳ￥ＸｉａｎｇＤｏｎｇＪＩＡＯ；ＪｉｎＷａｎｇＨＵＡＮＧ；ＪｕｎＦｅｎｇＬＩＵ；ＬｉａｎｇＮｉａｎＪＩ（...     

A NEW METHOD FOR PREPARATION OF IRON（Ⅲ） PORPHYRIN OXYANION COMPLEXES－SYNTHESIS OF PERCHLORATE（PORPHYINATO） IRON（Ⅲ）

ＡＮＥＷＭＥＴＨＯＤＦＯＲＰＢＥＰＡＲＡＴＩＯＮＯＦＩＢＯＮ（Ⅲ）ＰＯＲＰＨＹＲＩＮＯＸＹＡＮＩＯＮＯＭＰＬＥＸＥＳ－ＳＹＮＴＨＥＳＩＳＯＦＰＥＲＣＨＬＯＲＡＴＥ（ＰＯＲＰＨＹＩＮＡＴＯ）ＩＲＯＮ（Ⅲ）￥ＸｉｎＨｕａＺＨＯＮＧ；ＹａｏＹｕＦＥＮＧ；Ｊ...     

A NEW METHOD FOR PREPARATION OF IRON（Ⅱ） PORPHYRIN COMPLEX－ISOLATION AND CHARACTERIZATION OF AMINE COMPLEX OF FERROUS PORPHYRIN

ＡＮＥＷＭＥＴＨＯＤＦＯＲＰＲＥＰＡＲＡＴＩＯＮＯＦＩＢＯＮ（ＩＩ）ＰＯＲＰＨＹＲＩＮＣＯＭＰＬＥＸ－ＩＳＯＬＡＴＩＯＮＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦＡＭＩＮＥＣＯＭＰＬＥＸＯＦＦＥＲＲＯＵＳＰＯＲＰＨＹＲＩＮ￥ＸｉｎＨｕａＺＨＯＮＧ；Ｙ...     

A NEW METHOD OF PREPARATION OF IRON(II) PORPHYRIN COMPLEXES — ISOLATION AND CHARACTERIZATION OF BIS(N-BUTYLAMINE) IRON(II) PORPHYRIN

Abstract

Fe(II)T(p-X)PP(NH₂Bu ⁿ )₂ (X = H, Cl, CH₃, OCH₃, TPP = dianion of meso-tetraphenylporphyrin) complexes have been prepared by the reduction of Fe(III) porphrins with n-butylamine in antiformin/dichloromethane in air, and by sodium borohydride reduction. The complexes were characterized by electronic and IR spectra and elemental analysis.     

ESR SPECTRA STUDY OF COPPER(Ⅱ) COORDINATION COMPLEXES OF PYRIDI

The ESR spectra of powdered samples of Cu(Ⅱ) complexes with pyridine and its sixhomologues and pyrrol, aniline, as well as their solutions are measured at 77K in this paper.The electronic levels of these complexes are calculated from the ESR spectral parameters.It is found that the non-pyridine ligands of complexes which can be substituted by pyridinemolecules of solvent in solution of pyridine/chloroform form Py_4Cu~(2 ). A molecular configura-tion is proposed. for Py_4Cu~(2 ) in solution. It is shown that the treatment with D_(2h) symmetryinstead of D_(4h) symmetry leads to a more satisfactory explanation of the ESR spectra.     

AXIAL COORDINATION IN COBALT(II) COMPLEXES OF TWO SYNTHETIC MACROCYCLIC LIGANDS CONTAINING THE BIDENTATE α-DIIMINE GROUP

Abstract

In order to elucidate the nature of axial coordination in synthetic macrocyclic complexes of cobalt(II), we have synthesized two new series of such complexes, containing the macrocycles Me₄ [14] 1,3,8,10-tetraeneN₄ and Me₂ [14] 1,3-dieneN₄, by direct isolation of the Co(II) complexes from the condensation reaction mixtures. The complexes are formally five-coordinate in the solid state, but exhibit a tendency toward six-coordination in the presence of potential axial ligands, as demonstrated by electronic spectral and electron paramagnetic resonance studies. The Co(tetraeneN₄)⁺² and Co(dieneN₄)⁺² species are compared with the previously studied Co(Me₆ [14] 4, 11-dieneN₄)⁺² moiety with respect to axial coordination. It is concluded that the presence of methyl substituents on the six-membered chelate rings of the latter complex have a marked effect on its tendency to coordinate axial ligands.     

A NOVEL APPROACH FOR THE PREPARATION OF MEDIUM-SIZE LACTAMS

ＡＮＯＶＥＬＡＰＰＲＯＡＣＨＦＯＲＴＨＥＰＲＥＰＡＲＡＴＩＯＮＯＦＭＥＤＩＵＭ－ＳＩＺＥＬＡＣＴＡＭＳ￥ＹｕｎＸｉｎＢｏ；ＤｏｎｇＬｕＢＡＩ（ＳｈａｎｇｈａｉＩｎｓｔｉｔｕｔｅｏｆＭａｔｅｒｉａＭｅｄｉｃａ，ＣｈｉｎｅｓｅＡｃａｄｅｍｙｏｆＳｃｉｅｎ...     

STUDIES ON THE CATALYTIC BEHAVIORS OF SOME BIPOLYMER——PALLADIUM COMPLEXES FOR HYDRO-GENATION OF NITRO-COMPOUNDS AND OLEFINS

Some water-soluble bipolymer-Pd complexes were prepared. It was found that the bipolymer-Pd complexes exhibited remarkably higher catalytic activity and stability than that of the single polymer-Pd complex for hydrogenation of nitro-compounds and olefins under mild conditions.     

INVESTIGATION ON THE WATER－SOLUBLE YTTERBIUM PORPHYRIN PARTⅡ THE ELECTROCHEMICAL STUDY OF THE YTTERBIUM PORPHYRIN COMPLEX

ＩＮＶＥＳＴＩＧＡＴＩＯＮＯＮＴＨＥＷＡＴＥＲ－ＳＯＬＵＢＬＥＹＴＴＥＲＢＩＵＭＰＯＲＰＨＹＲＩＮＰＡＲＴⅡＴＨＥＥＬＥＣＴＲＯＣＨＥＭＩＣＡＬＳＴＵＤＹＯＦＴＨＥＹＴＴＥＲＢＩＵＭＰＯＲＰＨＹＲＩＮＣＯＭＰＬＥＸＱｉａｎＫｕｎＺＨＵＡＮＧ；Ｘｉａｏ...     

SPECTROPHOTOMETRIC STUDIES OF THE IRON CATALYST SYSTEM USED FOR BUTADIENE POLYMERIZATION

Catalysts consistiug of different iron compounds, triisobutylaluminium and warious ligands containing nitrogen used for butadiene polymerization were investigated by UV-visible, infrared spectroscopy. Spectra obtained illustrate an exchange taking place between the acetylacetonyl group in Fe(acac)_3 and the isobutyl group in Al(i-Bu)_3. During the exchange iron was reduced to lower valence state and coordinated with dipyridine or phenanthroline forming an active intermediate complex. A correlation between the absorption strength of the active intermediate complex in the visible range and the activity of catalyst was established.     

SOME REGULARITIES IN THE SYNTHESES AND STRUCTURE OF LINEAR MOLYBDENUM-IRON-SULFUR CLUSTER COMPLEXES

Linear Mo-Fe-S cluster complexes with basic unit of MoS_4 can be divided into four types ac-cording to the central Mo-S skeleton (S_2MoS_2Fe, S_2MoS_2FeS_2MoS_2, S_2MoS_2FeS_2Fe, FeS_2MoS_2Fe).Ten such complexes with various ligands and cations were synthesized, and their crystal structureswere determined and characterized by electron spin resonance, infrared and electron absorptions,Mossbauer and magnetic effects. Atomic distances from crystallographic analysis were comparedsystematically with respective spectroscopic data. There is strong evidence indicating that electrontransfers from Fe(Ⅱ) to Mo(Ⅵ), in spite of the fact that the apparent oxidation state of molyb-denum in most of the aforementioned complexes remains six. The probability of this electrontransfer depends strongly on the environment of Fe(Ⅱ). The fact that MoS_4~(2-) is both a goodbidentate ligand and an effective electron transfer unit is also evidence for its presence in manymolybdoenzymes and as a catalytically active center.     

HYBRID ZINC（Ⅱ） AND IRON（Ⅲ）PORPHYRIN DIMER：A NEW MODEL SYSTEM OF CYTOCHROME P450 TO HYDROXYLATE CYCLOHEXANE

ＨＹＢＲＩＤＺＩＮＣ（Ⅱ）ＡＮＤＩＲＯＮ（Ⅲ）ＰＯＲＰＨＹＲＩＮＤＩＭＥＲ：ＡＮＥＷＭＯＤＥＬＳＹＳＴＥＭＯＦＣＹＴＯＣＨＲＯＭＥＰ４５０ＴＯＨＹＤＲＯＸＹＬＡＴＥＣＹＣＬＯＨＥＸＡＮＥＺｈａｎＬｉａｎｇＬＩＵ，ＪｉｎＷａｎｇＨＵＡＮＯ，ＣａｉＬｉｎ...     

CARBONACEOUS PRODUCTS OF POLYMER-PALLADIUM COMPLEXES AS CATALYSTS FOR THE HYDROGENATION OF METHYL ACRYLATE

Many catalysts were pcrpared by carbonization of ion exchange resin-PdCl_2 complexes at high temperature in nitrogen, hydrogen atmosphere. The rates for the hydrogenation of methyl acrylate and the amounts of Pd elution of the carbonaceous products were measured and compared with those of commercial Pd/C catalyst. It indicates that the carbonaceous products are less active than Pd/C. However, the leaching of Pd from carbonaceous products is very small and much less than that from Pd/C.     

SYNTHESES OF POLYMER-BOUND RHODIUM COMPLEXES AND THEIR APPLICATION AS CATALYSTS FOR THE HYDROFORMYLATION OF DIISOBUTYLENE (Ⅱ)

Five kinds of polymer-anchored aminophosphine-rhodium complexes were synthesizedby ionic and covalent bonding methods. These anehored rhodium complexes synthesizedpossess good catalytic activity and aldehyde-formation selectivity in the hydroformylationof diisobutylene. The complexes anchored via covalent bonds on polymers showedexcellent reproducibility on recycling. After reaction, it indicated that the loss of rhodiumof the catalysts was very small as shown by analysis.     

STUDY ON THE SECOND HARMONIC GENERATION OF SOME LANTHANIDE(Ⅲ) COORDINATION COMPOUNDS

The measurements of second harmonic generation efficiencies of some coordination compounds of lanthanide(Ⅲ) carboxylates and β-diketonates have been reported. The results show thatmost of lanthanide cinnamate have SHG activity.     

THE CATALYTIC PROPERTIES OF POLY（2－VINYLPYRIDINE）AND ITS QUATERNARY AMMONIUM SALT BOUND Rh（Ⅰ） COMPLEXES FOR CARBONYLATION OF METHANOL

ＴＨＥＣＡＴＡＬＹＴＩＣＰＲＯＰＥＲＴＩＥＳＯＦＰＯＬＹ（２┐ＶＩＮＹＬＰＹＲＩＤＩＮＥ）ＡＮＤＩＴＳＱＵＡＴＥＲＮＡＲＹＡＭＭＯＮＩＵＭＳＡＬＴＢＯＵＮＤＲｈ（Ⅰ）ＣＯＭＰＬＥＸＥＳＦＯＲＣＡＲＢＯＮＹＬＡＴＩＯＮＯＦＭＥＴＨＡＮＯＬＬｉＸｉａｏｂ...     

STUDY ON NOVEL SORBENT FOR REMOVAL OF UREA COMPLEX SORPTION OF UREA BY MEANS OF ALGINATE—Cu（Ⅱ） COMPLEX

Alginate-Cu(Ⅱ）complex beads or membranes were prepared for removal of urea.The mechanism of sorption of urea was identified by UV-Visible spectra,FT-IR spectra and Far-Infrared spectra.The factors affecting the urea sorption capacity were discussed in detail.Results showed that the Alginate-Cu(Ⅱ）complex sorbent can sorb about 60 my urea per gram of sorbent at 37℃ and the concentration of urea was 130mg/100ml in Na2HPO4 and NaH2PO4 buffer solution(pH=7.0).