ine heterobinuclear complexes of Cu (Ⅱ)-RE (Ⅲ) with N, N′-bis-(3-car-boxylsalicylidene ) trimetliylenediamine (TS) were syntliesized and characterized bymeans of elemental analyses, molar conductivity, thermogravim...ine heterobinuclear complexes of Cu (Ⅱ)-RE (Ⅲ) with N, N′-bis-(3-car-boxylsalicylidene ) trimetliylenediamine (TS) were syntliesized and characterized bymeans of elemental analyses, molar conductivity, thermogravimetry,IR and elec-tronic spectra. The measurements of variable-temperature magnetic susceptibilitysliow that there exists only a very weak antiferromagnetic spin exchange interactionbetween the ions of Cut(Ⅱ) and RE(Ⅲ) in CuRETSCI . 3H_2O.展开更多
Eight novel heterobinuclear complexes of Ln3+ and Zn2+ with salicylidene diethylene glycol diamine(SALDA) Schiff base (NO3)22H2O(Ln=Pr, Nd, Sm, Gd, Tb, Er, Yb, Y) were synthesized and characterized on the basis of IR...Eight novel heterobinuclear complexes of Ln3+ and Zn2+ with salicylidene diethylene glycol diamine(SALDA) Schiff base (NO3)22H2O(Ln=Pr, Nd, Sm, Gd, Tb, Er, Yb, Y) were synthesized and characterized on the basis of IR and UV, particularly by1H and13C NMR spectra. It is confirmed that the azomethine nitrogen, ethereal oxygen and a part of phenolic oxygen atoms coordinate to the central ions.展开更多
Four new u-oxamido heterobinuclear complexes have been synthesized and identified as [Cu(oxap)Fe(L)2]SO4, where oxap denotes the N, N'-bis(2-aminopropyl)oxamido dianion and L represents diaminoethane (en); 1,3-dia...Four new u-oxamido heterobinuclear complexes have been synthesized and identified as [Cu(oxap)Fe(L)2]SO4, where oxap denotes the N, N'-bis(2-aminopropyl)oxamido dianion and L represents diaminoethane (en); 1,3-diaminopropane (pn); 1,2-diaminopropane (ap) and 2,9-dimethyl-1,10-phenanthroline (Me2-phen). Based on the elemental analyses, spectroscopic studies, magnetic moments (at room temperature) and molar conductivity measurements, extended oxamido-bridged structures consisting of a copper(Ⅱ) and an iron(Ⅱ) ions, which have a square planar environment and an octahedral environment, respectively, are proposed for these complexes. Complexes [Cu(oxap)Fe(en)2]SO4 (1) and [Cu(oxap)Fe(pn)2]SO4 (2) have been characterized by variable temperature magnetic susceptibility (4.2~300 K) and the observed data were least-squares fitted to the susceptibility equation derived from the spin Hamiltonian including single-ion zero-field interaction for the iron(Ⅱ) ion, H=-2JS1.S2-DSzl2, giving the exchange integrals J=-21.9 cm-1 for 1 and J=-23.6 cm-1 for 2. These results are commensurate with antiferromagnetic interactions between adjacent metal ions within each molecule.展开更多
Thiolate-bridged hetero-bimetallic complexes[Cp^(*)M(MeCN)N_(2)S_(2)FeCl][PF_(6)](2,M=Ru;3,M=Co,Cp^(*)=η^(5)-C_(5)Me_(5),N_(2)S_(2)=N,N'-dimethyl-3,6-diazanonane-1,8-dithiolate)were prepared by self-assembly of d...Thiolate-bridged hetero-bimetallic complexes[Cp^(*)M(MeCN)N_(2)S_(2)FeCl][PF_(6)](2,M=Ru;3,M=Co,Cp^(*)=η^(5)-C_(5)Me_(5),N_(2)S_(2)=N,N'-dimethyl-3,6-diazanonane-1,8-dithiolate)were prepared by self-assembly of dimer[N_(2)S_(2)Fe]2 with mononuclear precursor[Cp^(*)Ru(MeCN)_(3)][PF_(6)]or[Cp^(*)Co(MeCN)_(3)][PF_(6)]_(2)in the presence of CHCl_(3)as a chloride donor.Complexes 2 and 3 exhibit obviously different redox behaviors investigated by cyclic voltammetry and spin density distributions supported by DFT calculations.Notably,iron-cobalt complex 3 possesses versatile reactivities that cannot be achieved for complex 2.In the presence of CoCp_(2),complex 3 can undergo one-electron reduction to generate a stable formally Co^(II)Fe^(II)complex[Cp^(*)CoN_(2)S_(2)FeCl](4).Besides,the terminal chloride on the iron center in 3 can be removed by dehalogenation agent AgPF_(6)or exchanged with azide to afford the corresponding complexes[Cp^(*)Co(MeCN)N_(2)S_(2)Fe(MeCN)][PF_(6)]_(2)(5)and[Cp^(*)Co(MeCN)N_(2)S_(2)Fe(N_(3))][PF_(6)](6).In addition,complexes 2,3 and 4 show distinct catalytic reactivity toward the disproportionation of hydrazine into ammonia.These results may be helpful to understand the vital role of the heterometal in some catalytic transformations promoted by heteromultinuclear complexes.展开更多
The single crystal of [CuCo(TS)(H2O)·H2O],where TS is the schiff base N,N’ bis(3 carboxylsalidene)trimethylenediamine, was obtained and its crystal structure was determined by the single crystal X ray diffractio...The single crystal of [CuCo(TS)(H2O)·H2O],where TS is the schiff base N,N’ bis(3 carboxylsalidene)trimethylenediamine, was obtained and its crystal structure was determined by the single crystal X ray diffraction method at room temperature. It crystallizes in the monoclinic system, space group P21/c. The lattice parameters are a=11.855(2)?, b=14.722(3)?, c=12.080(2)?, β=117.32(3)°, V=1879.4(7)?3 , Z=4 with R1=0.0330. The structure is made of heterobinuclear units . The copper atom is coordinated by two nitrogens, two phenolic oxygens, in a square planar manner. And the cobalt atom is coordinated by two phenolic oxygen atoms, two equatorial carboxyl oxygen atoms and one axial water oxygen atom, in a distorted square pyramid. Two metal atoms are bridged by two phenolic oxygens. In the crystal packing, the neutral molecules built layers. Within these layers the molecules are connected through hydrogen bonds. And the thermal property of the complex according to crystal structure is also investigated.展开更多
合成了2,2′,2″-三氨基乙基胺(tren)Schiff碱和咪唑为配体的2个铜(Ⅱ)单核配合物[(tren)Cu](ClO4)2、[(tren)Cu-imH](ClO4)2,以及一个对称性的咪唑桥联铜锌异双核配合物[(tren)Cu im Zn(tren)](ClO4)3,用元素分析、摩尔电导、反射光谱...合成了2,2′,2″-三氨基乙基胺(tren)Schiff碱和咪唑为配体的2个铜(Ⅱ)单核配合物[(tren)Cu](ClO4)2、[(tren)Cu-imH](ClO4)2,以及一个对称性的咪唑桥联铜锌异双核配合物[(tren)Cu im Zn(tren)](ClO4)3,用元素分析、摩尔电导、反射光谱及磁化率测定对配合物的组成和结构进行了表征。采用循环伏安法分别研究了配合物在乙腈和水溶液中的电化学性质,研究表明:Zn(Ⅱ)能通过咪唑桥改变Cu(Ⅱ)接受电子的能力。在水溶液中咪唑桥异双核配合物较稳定,未发生断裂。展开更多
文摘ine heterobinuclear complexes of Cu (Ⅱ)-RE (Ⅲ) with N, N′-bis-(3-car-boxylsalicylidene ) trimetliylenediamine (TS) were syntliesized and characterized bymeans of elemental analyses, molar conductivity, thermogravimetry,IR and elec-tronic spectra. The measurements of variable-temperature magnetic susceptibilitysliow that there exists only a very weak antiferromagnetic spin exchange interactionbetween the ions of Cut(Ⅱ) and RE(Ⅲ) in CuRETSCI . 3H_2O.
文摘Eight novel heterobinuclear complexes of Ln3+ and Zn2+ with salicylidene diethylene glycol diamine(SALDA) Schiff base (NO3)22H2O(Ln=Pr, Nd, Sm, Gd, Tb, Er, Yb, Y) were synthesized and characterized on the basis of IR and UV, particularly by1H and13C NMR spectra. It is confirmed that the azomethine nitrogen, ethereal oxygen and a part of phenolic oxygen atoms coordinate to the central ions.
基金Project supported by the Natural Science Foundation of shandong Province and the National Natural Science Foundation of China.
文摘Four new u-oxamido heterobinuclear complexes have been synthesized and identified as [Cu(oxap)Fe(L)2]SO4, where oxap denotes the N, N'-bis(2-aminopropyl)oxamido dianion and L represents diaminoethane (en); 1,3-diaminopropane (pn); 1,2-diaminopropane (ap) and 2,9-dimethyl-1,10-phenanthroline (Me2-phen). Based on the elemental analyses, spectroscopic studies, magnetic moments (at room temperature) and molar conductivity measurements, extended oxamido-bridged structures consisting of a copper(Ⅱ) and an iron(Ⅱ) ions, which have a square planar environment and an octahedral environment, respectively, are proposed for these complexes. Complexes [Cu(oxap)Fe(en)2]SO4 (1) and [Cu(oxap)Fe(pn)2]SO4 (2) have been characterized by variable temperature magnetic susceptibility (4.2~300 K) and the observed data were least-squares fitted to the susceptibility equation derived from the spin Hamiltonian including single-ion zero-field interaction for the iron(Ⅱ) ion, H=-2JS1.S2-DSzl2, giving the exchange integrals J=-21.9 cm-1 for 1 and J=-23.6 cm-1 for 2. These results are commensurate with antiferromagnetic interactions between adjacent metal ions within each molecule.
基金supported by the National Natural Science Foundation of China(Nos.21690064,22001031)the key laboratory of Bio-based Chemicals of Liaoning Province of China+1 种基金the“111”project of the Ministry of Education of Chinathe Fundamental Research Funds for the Central Universities(No.DUT19RC(3)013)。
文摘Thiolate-bridged hetero-bimetallic complexes[Cp^(*)M(MeCN)N_(2)S_(2)FeCl][PF_(6)](2,M=Ru;3,M=Co,Cp^(*)=η^(5)-C_(5)Me_(5),N_(2)S_(2)=N,N'-dimethyl-3,6-diazanonane-1,8-dithiolate)were prepared by self-assembly of dimer[N_(2)S_(2)Fe]2 with mononuclear precursor[Cp^(*)Ru(MeCN)_(3)][PF_(6)]or[Cp^(*)Co(MeCN)_(3)][PF_(6)]_(2)in the presence of CHCl_(3)as a chloride donor.Complexes 2 and 3 exhibit obviously different redox behaviors investigated by cyclic voltammetry and spin density distributions supported by DFT calculations.Notably,iron-cobalt complex 3 possesses versatile reactivities that cannot be achieved for complex 2.In the presence of CoCp_(2),complex 3 can undergo one-electron reduction to generate a stable formally Co^(II)Fe^(II)complex[Cp^(*)CoN_(2)S_(2)FeCl](4).Besides,the terminal chloride on the iron center in 3 can be removed by dehalogenation agent AgPF_(6)or exchanged with azide to afford the corresponding complexes[Cp^(*)Co(MeCN)N_(2)S_(2)Fe(MeCN)][PF_(6)]_(2)(5)and[Cp^(*)Co(MeCN)N_(2)S_(2)Fe(N_(3))][PF_(6)](6).In addition,complexes 2,3 and 4 show distinct catalytic reactivity toward the disproportionation of hydrazine into ammonia.These results may be helpful to understand the vital role of the heterometal in some catalytic transformations promoted by heteromultinuclear complexes.
文摘The single crystal of [CuCo(TS)(H2O)·H2O],where TS is the schiff base N,N’ bis(3 carboxylsalidene)trimethylenediamine, was obtained and its crystal structure was determined by the single crystal X ray diffraction method at room temperature. It crystallizes in the monoclinic system, space group P21/c. The lattice parameters are a=11.855(2)?, b=14.722(3)?, c=12.080(2)?, β=117.32(3)°, V=1879.4(7)?3 , Z=4 with R1=0.0330. The structure is made of heterobinuclear units . The copper atom is coordinated by two nitrogens, two phenolic oxygens, in a square planar manner. And the cobalt atom is coordinated by two phenolic oxygen atoms, two equatorial carboxyl oxygen atoms and one axial water oxygen atom, in a distorted square pyramid. Two metal atoms are bridged by two phenolic oxygens. In the crystal packing, the neutral molecules built layers. Within these layers the molecules are connected through hydrogen bonds. And the thermal property of the complex according to crystal structure is also investigated.
文摘合成了2,2′,2″-三氨基乙基胺(tren)Schiff碱和咪唑为配体的2个铜(Ⅱ)单核配合物[(tren)Cu](ClO4)2、[(tren)Cu-imH](ClO4)2,以及一个对称性的咪唑桥联铜锌异双核配合物[(tren)Cu im Zn(tren)](ClO4)3,用元素分析、摩尔电导、反射光谱及磁化率测定对配合物的组成和结构进行了表征。采用循环伏安法分别研究了配合物在乙腈和水溶液中的电化学性质,研究表明:Zn(Ⅱ)能通过咪唑桥改变Cu(Ⅱ)接受电子的能力。在水溶液中咪唑桥异双核配合物较稳定,未发生断裂。
