SYNTHESIS OF POLYMER—SUPPORTED PALLADIUM CATALYSTS AND THEIR CATALYTIC BEHAVIOR FOR THE SELECTIVE HYDROGENATION OF MESITYL OXIDE

Copolymer of styrene-divinylbenzene in bead from was made by suspension polymerization.After chloromethylation and amination,five kinds of polymeric amines were thus obtained.These polymers were reacted with palladium chloride,and were then reduced.The polymer-supported catalysts synthesized above were used to catalyze the selective hydrogenation of mesityl oxide under reaction conditions of 80℃ and 10kg/cm^2,using methanol as a solvent.The catalytic activity and MIBK(methyl isobutyl ketone) formation selectivity of the catalysts were examined.     

SYNTHESES OF POLYMERIC LIGAND-BOUND RHODIUM COMPLEXES AND THEIR CATALYTIC APPLICATION FOR THE HYDROFORMYLATION OF DIISOBUTYLENE

Ten polymeric ligand bound rhodium complexes were synthesized by the reaction ofRh_2(CO)_4Cl_2 and functional cross-linked poly-styrene consisting of amine, aminophosphine andphosphite groups. These polymeric catalysts were used for hydroformylation of diisobuty-lene at a temperature of 110℃, under pressures of 100, 80, 60 kg/cm~2 and H_2/CO = 1: 1 for 6h, benzene being used as the solvent. Most of the catalysts prepared showed good catalyticproperties. IR spectral analysis indicates that the polymeric amine bound rhodium catalystspossess a polydentatc structure. The rhodium elution of the catalysts was examined. Therelationship between the structure of ligands, the rhodium elution and catalytic activity wasdiscussed. A curve of rhodium elution v.s. the number of catalytic application cycles wasinvestigated. The influence of reaction conditions and additives on the loss of rhodium wasalso studied. The possible mechanism of rhodium elution of the polymeric catalysts wassuggested.     

C-H BOND ACTIVATION AND FUNCTIONALIZATION OF METHANE UNDER MILD CONDITIONS

In the presence of Rh(COD)(dppe)Cl (COD=1, 5-cyclootadiene, dppe=1,2-bis-(diphenylphosphino)ethane) and CO, we studied the H/Cl exchange reaction between CH_4 and o-dichlorobenzene, and observed that the active species of the reaction is a complex containing dppe and carbonyl ligands. We suggest that the mechanism of exchange reaction may be described by the elementary reaction of oxidative addition and reductive elimination. In the presence of trans-PtHL_2X (L=PEt_3, P(n-Pr)_3, P(n-Bu)_3, PPh_3; X=Cl~-, Br~-, I~-, CN~-) complexes, we have studied the oxidative chlorination reaction of methane. The catalytic activity was found to be related to the electron-donating properties and the cone angle of tertiary phosphine, as well as the trans-effect of X anionic ligands. In addition to the above reactions, we have also studied the insertion reaction of acetylene into C-H bond of methane catalyzed by organotransition-metal complexes containing heterocyclic chelate ligands, such as bipy, phen and TMEDA, in DMF     

Peroxo Complexes of Molybdenum(VI) Containing Mannich Base Ligands

The molybdenum(VI)-peroxo complexes containing Mannich base ligands having a formula as [MoO(O2)2(L-L)] [where L-L＝morpholinobenzyl benzamide (MBB), piperidinobenzyl benzamide (PBB), morpholinobenzyl urea (MBU), piperidinobenzyl urea (PBU), morpholinobenzyl thiourea (MBTU), piperdinobenzyl thiourea (PBTU)] have been synthesized and characterized by physico-chemical, electrochemical techniques and TGA/DTA studies. The complexes have been prepared by stirring ammonium molybdate and excess of 30% aqueous-H2O2 and then treatment with ethanolic solution of the ligand. Studies revealed that these complexes were non-electrolytes and diamagnetic in nature. The ligands are bound to metal in a bidentate mode through carbonyl oxygen/thiocarbonyl sulphur and the ring nitrogen. The cyclic voltammograms of the complexes show two quasi-reversible steps involving complexes. The complexes have also been tested for antibacterial activity against Salmonella and Kleibsella. The antibacterial study of the ligands and complexes indicate that the complexes exhibit higher activity than the free ligands.     

Synthesis and Thermal Rearrangement of Tetramethyldisilane-bridged Bis(cyclopentadienyl) Diiron Complexes with Bis(phosphine)Substitution

Photolysis of [Me2SiSiMe2)[C5H4Fe(CO2)]2with a series of bis(phosphine)ligands Ph2P(CH2)n PPh2(n=1-4) leads to the formation of the corresponding diiron complexes with intramolecular and intermolecular bis(phosphine) substitution.When these complexes were heated in refluxing xylene.only in the complexes with intermolecular bis(phosphine )substitution the thermal rearrangement reaction occurred.     

PREPARATION OF NONIONIC WATER-SOLUBLE PHOSPHINES AND THEIR RHODIUM COMPLEXES FOR CATALYTC HYDROFORMYLATION OF OLEFIN

Two kinds of nonionic water-soluble phosphine complexes:tri(o-polyglycol ether phenyl) phosphine(Ⅰ) and tri(p-polyglycol ether phenyl)phosphine(Ⅱ) (n=3～12) were prepared. Their thodium complexes preparedin sitn were used in aqueous/organic solvent two-phase system for catalytichydroformylation of olefin. The results implied that the surfactant phosphineligands for the biphasic hydroformylation of olefin shows good catalytic activityand selectivity,At 100 C and 6.0 MPa total pressure (CO/H_2=1:1) theconversion of (?) dodecene and selectivity to aldehyde were higher than 85%.The effects of different conditions on the hydrofurmylation reaction wereexamined.     

SYNTHESIS AND CHARACTERIZATION OF BIS-[2-[[(2-ALKOXYPHENYL)IMINO]METHYL]-PHENOLATO-O,N,O]NICKEL(II)COMPLEXES AND THEIR NORBORNENE POLYMERIZATION

A series of salicylaldimines,synthesized in high yield via microwave-assisted condensation of salicylaldehyde and 2-alkoxyaniline were allowed to react with nickel chloride to form six-coordinated nickel complexes.These nickel complexes were carefully characterized,and the solid structure of la was elucidated by X-Ray diffraction.Activated with MAO,the nickel complexes showed good activity for homopolymerization of norbornene.Reaction parameters,such as the ratio of nickel precursor to MAO,monomer concentration,reaction time and the reaction temperature,as well as the nature of the ligands were found to have significant effects on the catalytic activity and some properties of the resulting polynorbornene.     

HYDROFORMYLATION OF 1-HEXENE WITH Rh_4(CO)_(12) AND [Rh(CO)_2Cl]_2

The hydroformylation of hexene-1 catalyzed by Rh_4 (CO)_12 and 〔Rh(CO)_2Cl〕_2 andthe effects of solvents (benzene, n-heptane and THF) and PPh_3 on the activity andselectivity of the catalysts were studied.The results indicated that the activity of Rh_4(CO)_(12) decreased with increasing solventpolarity and it did not change appreciably with addition of PPh_3 when the molar ratioPPh_3/Rh_4(CO)_(12)≤4. Thc activity of Rh_4(CO)_(12) was over twice as large as that of〔Rh(CO)_2Cl〕_2 when calculated according to the number of moles of rhodium clusters inbenzene without PPh_3, but the activities of both Rh_4(CO)_(12) and 〔Rh(CO)_2Cl〕_2 wereabout the same when calculated according to the number of rhodium atoms. It is suggestedthat the clusters probably dissociated into the similar active rhodium mononuclear speciesunder the reaction conditions and the species formed a cluster similar to Rh_4(CO)_(12) againwhen the conditions were reduced to the ambient temperature and pressure.     

ELECTROCARBOXYLATION OF ORGANIC COMPOUNDS WITH CARBON DIOXIDE CATALYZED BY METALLOPORPHYRINS(Ⅰ)——CATALYTIC ACTIVITIES OF METALLOPORPHYRINS FOR ELECTROCARBOXYLATION OF BENZYL CHLORIDE

The electrocarboxylation of benzyl chloride with CO_2 catalyzed by metalloporphyrins and the effects of different kinds of central metals and ligands on catalytic activities are reported. These metalloporphyrins whose central metals can form corresponding M (Ⅰ) complexes such as CoTPP, FeTPP have high activities. With water-soluble porphyrin ligands such as TPPS, TTMAPI, the corresponding metalloporphyrins have high catalytic activity. Electron-with-drawing groups on the porphyrin ring cause the lowering of activity.     

New Transition and Actinide Metal Complexes of 2‐Carboxy‐phenylhydrazo‐Benzoylacetone Ligand: Synthesis,Characterization and Biological Study

A new series of binary mononuclear complexes were prepared from the reaction of the hydrazone ligand, 2-carboxyphenylhydrazo-benzoylacetone (H2L), with the metal ions, Cd(II), Cu(II), Ni(II), Co(II), Th(IV) and UO2(VI). The binary Cu(II) complex of H2L was reacted with the ligands 1,10-phenanthroline or 2-aminopyridine to form mixed-ligand complexes. The binary complexes of Cu(II) and Ni(II) are suggested to have octahedral configurations. The Cd(II) and Co(II) complexes are suggested to have tetrahedral and/or square-planar geometries, respectively. The Th(IV) and UO2(VI) complexes are suggested to have octahedral and dodecahedral geometries, respectively. The mixed-ligand complexes have octahedral configurations. The structures of all complexes and the corresponding thermal products were elucidated by elemental analyses, conductance, IR and electronic absorption spectra, magnetic moments, 1H NMR and TG-DSC measurements as well as by mass spectroscopy. The ligand and some of the metal complexes were found to activate the enzyme pectinlyase.     

PREPARATION AND CATALYTIC BEHAVIOUR OF POLYMER-BOUND METALLOPORPHYRIN IN HYDROGENATION OF OLEFIN

The meso- tetraarylporphyrin has been anchored to styrene- divinylbenzenecopolymers by reaction of meso- tetra (4-hydroxylphenyl ) porphyrin with chloromethylatedresin under mild condition. A number of polymer transition metal complexes have beenprepared with the polymer ligand and metal salts. The polymeric ligand and its complexeshave been characterized by electronic spectra, and vibrational spectra. Cyclohexene can behydrogenated with the polymeric porphyrin palladium complex(P-THPPPd) as catalyst,and its catalytic activity was influenced by the polarity of solvents, the contents of water inethanol or reaction temperature. However, its catalytic activity was lower for nitro groups,carbonyl groups and olefins with steric hindrance substituents, and showed no activity foraromatic rings under these conditions.     

SYNTHESIS OF DI（ETHYLMERCAPTOETHYL） AMINO GROUP—CONTAINING POLYSESQUISILOXANE PLATINUM COMPLEX AND ITS CATALYSIS IN HYDROSIL YLATION OF OLEFINS WITH TRIETHOXYSILANE

Three new polysesquisiloxane-bound platinum complexes were synthesized via hydrolysis of N,N-di(β-ethylmercaptoethyl)γ-(triethoxysilyl)propylamine or cohydrolysis of the monomer with dodecyltriethoxysilane or with phenylpropylthiethoxysilane and immobilixation on fumed silica,followed by reacting with potassium platinite in acetone under argon atmosphere.The platinum complexes exhibited high catalytic activity for the hydrosilylation of olefins by triethoxysilane. The effects of temperature and the amount of complex on the catalytic activity,as well as the recovery and reusability of the catalysts were investigated.     

Dinuclear Nickel(Ⅱ) Chlorides Bearing N,N′-bis(5,6,7-trihydroquinolin-8-ylidene)-[1,1′-biphenyl]-4,4′-diamines: Synthesis and Ethylene Polymerization

5,6,7-Trihydroquinolin-8-one was condensed with the corresponding benzidine to give N,N′-bis(5,6,7-trihydroquinolin-8-ylidene)-[1,1′-biphenyl]-4,4′-diamine derivatives(L1–L3). The ligands were reacted with two equivalents of Ni Cl_2·6H_2O in a mixture of Et OH and CH_2Cl_2 to afford the corresponding dinickel(II) chloride complexes(Ni1-Ni3). The organic compounds were completely characterized, whilst the bi-metallic complexes were characterized by FTIR spectra and elemental analysis. These nickel complexes exhibited high activities towards ethylene polymerization in the presence of either MAO or Me_2AlCl, maintaining a high activity over a prolonged period. The obtained polyethylenes were confirmed as having low molecular weights by GPC analysis.     

Reactions and crystal structures of heterodinuclear complexes R3Sn-M（CO）5 （M = Mn, Re） with some nitrogen ligands

Some reactions of R_3SnM(CO)_5(M = Mn,Re) with CH_3CN or pyridine were investigated to give complexes R_3SnMn(CO)_3LL′or R_3SnMn(CO)_4L by a facile mild method.X-ray diffractions analyses show that,in contrast to the phosphine ligand occupying in axial position,nitrogen ligands occupy equatorial position.     

取代四甲基环戊二烯基钌羰基化合物的合成及晶体结构(英文)

The ligands (C5Me4R) [R =n-Butyl (1), Benzyl (2), PhMe-2 (3)] reacted with Ru3(CO)12 in refluxing xylene to give corresponding new substituted tetramethylcyclopentadienyl diruthenium metal carbonyl complexes [(η5-C5Me4R)Ru(CO)( μ-CO)]2 [R=n-Butyl (4), Benzyl (5), PhMe-2 (6)], respectively. The three new complexes were characterized by elemental analysis, IR and 1H NMR spectra. The crystal structure of complex 5 was determined by single crystal X-ray diffraction. The X-ray crystal structure of complex 5 confirms the structure with bridging and terminal CO groups. CCDC: 709601.     

Preparation of nanometer FeCuP alloy and its application in decomposition of PH3

A new ternary Fe-based alloy catalyst FeCuP applied to decompose PH_3 was prepared with low-cost material by chemical reduction deposition method.The properties of it were characterized by XRD,ICP and SEM.Its catalytic activity on the decomposition of PH_3 and the decomposition conditions were studied.FeCuP alloy exhibits high thermal stabilities and high catalytic activity.Using it as catalyst,the decomposition temperature of phosphine decreases from over 800℃to 400-500℃.The decomposition rate of phosphine achieved 100%.     

SYTHESE AND REACTIONS OF HETEROBINUCLEAR COMPLEXES [PhCl_2SnM(Cl)(CO)_3(CH_3CN)_2] (M = Mo, W)

Abstract The complexes [M(CO)_3(CH_3CN)_3](M=Mo, W)react with an equimolar quantity ofPhSnCl_3 in dichloromethane at room tempreture to afford new heterobinuclearcomplexes [PhCl_2SnM(Cl)(CO)_3(CH_3CN)_2] [M=Mo(1); W(2)]. The complexes reactwith two equivalents of PR_2R'(R=Ph, R'=Ph, Me; R=Cy, R'=H) to yield stablecomplexes [PhCl_2SnM(Cl)(CO)_3(PR_2R')_2]. Reaction of[PhCl_2SnM(Cl)(CO)_3(CH_3CN)_2]with one equivalent of PPh_2(CH_2)nPPh_2(n=I,2) or bulky phosphine ligands PBu_2~tClin dichloromethane at room tempreture to give [PhCl_2SnMo(Cl)(CO)_3{PPh_2(CH_2)n-PPh_2}] .CH_2Cl_2, [PhCl_2SnMo(Cl)(CO)_3PBu_2~tCl]. CH_2Cl_2, respectively. The complexes1 and 2 react with phosphite donor ligands P(OMe)_3 to give [PhCl_2SnM(Cl)(CO)_2-{P(OMe)_3}_3]. All complexes have been characterized by elemental analysis, IRand ~1HNMR spectroscopies. Here we report the preliminary results of this work.     

Mono-and Binuclear Cobalt(Ⅱ) Complexes Supported by Quinoline-2-imidate Ligands:Synthesis,Characterization,and 1,3-Butadiene Polymerization

A series of mono-and binuclear Co(II) complexes(Co1–Co7) supported by quinoline-2-imidate ligands were synthesized and thoroughly characterized.Measured by single crystal X-ray crystallography,complexes Co1 and Co3 adopted distorted tetrahedral structures around the cobalt center.Upon activation by ethylaluminium sesquichloride(EASC),these cobalt complexes exhibited high catalytic activity and cis-1,4-selectivity towards 1,3-butadiene polymerization.The effects of ligand environment,polymerization temperature,and cocatalyst types on the polymerization were investigated in detail.Interestingly,the binuclear Co(II) complexes exhibited high thermal stability,and the polymer yields were up to 97.2% even at a high temperature of 70 °C.     

Synthesis of a New Type of Amphilic and Water—soluble Tertiary Phosphine Ligands Substituted by an Ethoxylated Phosphonic Acid Chain and Their Palladium Complexes

The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N-(CH2PPh)22(n=1,2,3) were prepared by a new and simple route under mild conditions in good yield; the palladium (Ⅱ） complexes of the ligands 3a-c with 2:1 or 4:1 -PPh2 to Pd^2 molar ratio were also prepared and characterized.     

EFFECTS OF CONFORMATION OF POLYMER LIGANDS IN COPPER(Ⅱ) COMPLEXES ON CATALYLIC ACTIVITIES AND MECHANISM OF OXIDATIVE COUPLING OF β-NAPHTHOL

Copper(Ⅱ) complexes of sericin, chitosan, 6-and 2-aminodeoxystarch were used as catalysts in oxidative coupling of β-naphthol, the effects of conformation of the polymer ligands in these complexes on activities of the catalysts and mechanisms of the reaction were studied. It was found that if the catalysts react with the substrate by mechanism similar to the enzymic catalysis they must be composed of polymer ligands with highly coiled, especially with densely helicoidal, conformations. While catalysts composed of loosely coiled or helicoidal hgands react with the substrate through molecular collision and have relatively lower activities only. Under nitrogen, catalysts from sericin and chitosam reacting with β-naphthol give optically active β-binaphthol, rotating polarized light to right, but the stereoselectivities are rather low.