Heterogeneous catalytic aerobic oxidation behavior of Co–Na heterodinuclear polymeric complex of Salen-crown ether

A new kind of Co–Na heterodinuclear polymer complex based on Salen Schiff base and crown ether has been successfully prepared by condensation polymerization. Its catalytic behavior for aerobic oxidation of cyclohexene, alkylbenzenes and linear aliphatic olefins was studied in the absence of any solvents or reducing agents under mild conditions. The oxidation of cyclohexene catalyzed by the above catalyst proved to be a simple and efficient method for obtaining 2-cyclohexen-1-one (CO) and 2-cyclohexen-ol (OH) in a high selectivity. Kinetics of the oxidation was also investigated. The results showed that the aerobic oxidation of cyclohexene catalyzed by Salen-crown ether heterodinuclear polymer complex follows a radical chain aerobic oxidation mechanism. This oxidation system is also efficient in the oxidation of alkylbenzenes and linear aliphatic olefins, which afforded corresponding benzylic oxidation products and epoxides, respectively.     

一种新奇的d-f异双核配合物[Fe(phen)_3]_2[FeCe(tiron)_3]·6H_2O的水热合成、晶体结构和磁性

硝酸铁,硝酸铈,邻菲咯啉(phen)和钛铁试剂(Tiron)通过水热方法合成了一种d-f异双核配合物[Fe(phen)3]2[FeCe(tiron)3]·6H2O,tiron=C6H2O8S2。X-射线单晶衍射分析表明,晶体属立方晶系,P213空间群,晶胞参数为:a=2.19409(4)nm,V=10.5624(3)nm3,Z=4,F(000)=4648,R1=0.0451,wR2=0.1077,S=1.072。在具有C3对称性的[FeCe(tiron)3]6-单元中,Fe髥与6个酚氧配位形成一个反三棱柱配位多面体,Ce髥则与3个桥联的酚氧μ2-O和3个磺酸基的氧形成另一个与FeO6共用底面的反三棱柱配位多面体CeO6。配阳离子通过phen-phen之间的π-π相互作用和与配阴离子间的静电引力等作用组装成一种三角梅状准主/客体型的超分子。在2~300K温度范围内测试了配合物的变温磁化率,结果表明,Ce髥-Fe髥之间存在典型的反铁磁性相互作用。     

Syntheses and characterization of a new class of mono‐ and heterodinuclear derivatives of boron derived from Schiff bases

Reactions of 2‐isopropoxy‐1, 3, 2‐ benzodioxaborole with equivalent amounts of Schiff base ligands having two hydroxyl groups ( 1a–3a ) yield mononuclear derivatives with one residual hydroxy group. The reactions of these mononuclear derivatives with hexamethyldisilazane in a 2:1 ratio yield heterodinuclear derivatives. All these newly synthesized derivatives have been characterized by elemental analyses and molecular weight measurements. Tentative structures have been proposed on the basis of IR and NMR (¹H, ¹³C, ¹¹B,²⁹Si)spectral data and Fab‐mass studies. Schiff bases and their corresponding mono‐ and heterodinuclear derivatives of boron have also been screened for antifungal activities. Copyright © 2010 John Wiley & Sons, Ltd.     

Investigation on the thermal decomposition some heterodinuclear NiII-MII complexes prepared from ONNO type reduced Schiff base compounds ( M II=ZnII, CdII)

N,N′-bis(salicylidene)-1,3-propanediamine (LH₂), N,N′-bis(salicylidene)-2,2′-dimethyl-1,3-propanediamine (LDMH₂), N,N′-bis(salicylidene)-2-hydroxy-1,3-propanediamine (LOH₃), N,N′-bis(2-hydroxyacetophenylidene)-1,3-propanediamine (LACH₂) and N,N′-bis(2-hydroxyacetophenone)-2,2′-dimethyl-1,3-propanediamine (LACDMH₂) were synthesized and reduced to their phenol-amine form in alcoholic media using NaBH₄ (L^HH₂, LDM^HH₂, LOH^HH₂, LAC^HH₂ and LACDM^HH₂). Heterodinuclear complexes were synthesized using Ni(II), Zn(II) and Cd(II) salts, according to the template method in DMF media. The complex structures were analyzed using elemental analysis, IR spectroscopy, and thermogravimetry. Suitable crystals of only one complex were obtained and its structure determined using X-ray diffraction, NiLAC^H·CdBr₂·DMF₂, space group orthorhombic, Pbca, a=20.249, b=14.881, c=20.565 ? and Z=8. The heterodinuclear complexes were seen to be of [Ni·ligand·MX₂·DMF₂] structure (ligand=L^H2−, LDM^H2−, LOH^H2−, LAC^H2−, LACDM^H2−, M=Zn^II, Cd^II, X=Br⁻, I⁻). Thermogravimetric analysis showed irreversible bond breakage of the coordinatively bonded DMF molecules followed by decomposition at this temperature.     

Establishment of heterodinuclear replacement complexation and its application to direct determination of iron in natural water with dibromo-o-nitrophenylfluorone

The chromophore dibromo-o-nitrophenylfluorone (DBNPF) was used to complex Fe(III) and Cu(II) at pH 5.88. Fe(III) can competitively replace Cu(II) from its dinuclear complex Cu(DBNPF)Cu, and forms the Cu(DBNPF)Fe heterodinuclear complex. The Fe-DBNPF and Cu-DBNPF complexes were also characterized by the spectral correction technique. The heterodinuclear replacement complexation (HRC) is proposed and first used for the quantitative detection of iron in trace level with high sensitivity and good selectivity by the light-absorption ratio variation approach. The limit of detection of Fe is 1.0 μg L⁻¹. The method has been successfully applied to the direct determination of Fe(II, III) dissolved and bound to suspended substances in natural water.     

一种新奇的d-f异双核配合物[Fe(phen)3]2[FeCe(tiron)3]·6H2O的水热合成、晶体结构和磁性

硝酸铁,硝酸铈,邻菲咯啉(phen)和钛铁试剂(Tiron)通过水热方法合成了一种d-f异双核配合物 [Fe(phen)₃]₂[FeCe(tiron)₃]·6H₂O,tiron=C₆H₂O₈S₂。X-射线单晶衍射分析表明,晶体属立方晶系,P2₁3空间群,晶胞参数为：a=2.194 09(4) nm,V=10.562 4(3) nm³,Z=4,F(000)=4 648,R₁=0.045 1,wR₂=0.107 7,S=1.072。在具有C₃对称性的[FeCe(tiron)₃]^6-单元中,Fe(Ⅲ)与6个酚氧配位形成一个反三棱柱配位多面体,Ce(Ⅲ)则与3个桥联的酚氧μ₂-O和3个磺酸基的氧形成另一个与FeO₆共用底面的反三棱柱配位多面体CeO₆。配阳离子通过phen-phen之间的π-π相互作用和与配阴离子间的静电引力等作用组装成一种三角梅状准主/客体型的超分子。在2～300 K温度范围内测试了配合物的变温磁化率,结果表明, Ce(Ⅲ)-Fe(Ⅲ)之间存在典型的反铁磁性相互作用。     

Zur Reaktivität isomerer Heterodinuclearer Fischer-Carben-Komplexe mit Titanaoxetan- und Titanaoxolenteilstrukturen — Cycloreversions- und Insertionsreaktionen

Studies on the Reactivity of Isomeric Heterodinuclear Fischer-Carbene Complexes exhibiting a Titanaoxetan or Titanaoxolen Substructure – Cycloreversion and Insertion Reactions The reactivity of isomeric four- and five-membered carbene complexes Cp*₂ 3 and Cp*₂ 4 [ML_n: Cr(CO)₅ ( a ); W(CO)₅ ( b ); Cp*: C₅(CH₃)₅] has been investigated. A cycloreversion reaction, unusual for common metallaoxetanes, is found to dominate the chemical behaviour of 3 . The generation of vinylidene fragment [Cp*₂Ti?C?CH₂] 2 as an intermediate is proved either by trapping with ethylene and isocyanate or by protonation of the α-carbon atom. On the other hand no cycloreversion is observed for the titanaoxolene carbene complexes 4 . Ringenlargement is found by the reaction of 3 and 4 with isonitriles under formation of iminoacyl complexes. Accordingly 2,6-dimethylphenylisonitrile reacts with 3 b forming Cp*₂ 12 [Ar: 2,6-(CH₃)₂? C₆H₃]. A reversible insertion of cyclohexylisonitrile in 4a leads to isolation of the six-membered metallacycle Cp*₂ 16 (Cy: C₆H₁₁).     

Synthesis,Characterization and Magnetic Studies of μ‐Oxamido Copper (II) ‐ Chromium (III) Heterodinuclear Complexes

Three new μ‐oxamido‐bridged heterodinuclear copper (II)‐chromium (III) complexes formulated [Cu(Me₂oxpn)Cr‐(L)₂](NO₃)₃, where Me₂oxpn denotes N,N'‐bis(3‐amino‐2, 2‐dimethylpropyl)oxamido dianion and L represents 5‐methyl‐1,10‐phenanthroline (Mephen), 4,7‐diphenyl‐1,10‐phenanthroline (Ph₂phen) or 2,2′‐bipyridine (bpy), have been synthesized and characterized by elemental analyses, IR and electronic spectral studies, magnetic moments of room‐temperature and molar conductivity measurements. It is proposed that these complexes have oxamido‐bridged structures consisting of planar copper (II) and octahedral chromium (III) ions. The variable temperature magnetic susceptibilities (4.2–300 K) of complexes [Cu(Me₂oxpn)Cr(Ph₂phen)₂](NO₃)₃ (1) and [Cu(Me₂oxpn)Cr(Mephen)₂] (NO₃)₃ (2) were further measured and studied, demonstrating the ferromagnetic interaction between the adjacent chromium (III) and copper (II) ions through the oxamido‐bridge in both complexes 1 and 2. Based on the spin Hamiltonian, ? = ‐ 2J?₁ · ?₂, the exchange integrals J were evaluated as + 21.5 an^?1 for 1 and + 22.8 cm^?1 for 2.     

含二（二苯基膦）甲烷配体的钯—铑异双金属配合物的XPS能谱研究

研究了４种带ｄｐｐｍ〔二（二苯基膦）甲烷〕桥配体的钯－铑异双金属配合物的ＸＰＳ谱，得到了在配合物生成过程中Ｐｄ、Ｒｈ及Ｃｌ结合能的变化，揭示了它们所处的化学环境，解释了这４种配合物生成过程中所发生的配体迁移、氧化还原及金属－金属成键过程。     

基于草酰胺配体的新型异双核配合物的合成及其晶体结构

以草酰胺铜配合物CuL(H₂L=2,3-二氧-5,6 :13,14-二联苯基-9,10-环己基-1,4,8,11-四氮杂十四环-7,12-二烯烃)为前驱配体,1,10-邻菲啰啉为端接配体,高氯酸锰为金属核心,经回流反应合成了一个新型的异双核配合物［CuLMn(phen)₂］(ClO₄)₂·2CH₃OH(1),其结构和性能经UV-Vis, IR,元素分析,X-射线粉末衍射和X 射线单晶衍射表征。结果表明：1(CCDC: 1 445 582)属三斜晶系,空间群P-1,晶胞参数a=11.298(19) , b=15.17(4) , c=16.71(3) ,α=113.69(3), β=109.30(2), γ=93.08(4), V=2 417(9) ³, Z=2。 1在DMF中的最大吸收峰位于272 nm和361 nm。