Homogeneous solution of poor soluble aza bridged bis phenanthroline macrocyclic compound(H 2HAPP) was obtained by adding K 2CO 3 to its trifluoroacetate in CH 3OH CH 2Cl 2[ V (CH 3OH)∶ V (CH 2Cl 2)= 1∶1] solution. C...Homogeneous solution of poor soluble aza bridged bis phenanthroline macrocyclic compound(H 2HAPP) was obtained by adding K 2CO 3 to its trifluoroacetate in CH 3OH CH 2Cl 2[ V (CH 3OH)∶ V (CH 2Cl 2)= 1∶1] solution. Coordination reaction between H 2HAPP and metal ion Zn(Ⅱ) in CH 3OH CH 2Cl 2[ V (CH 3OH)∶ V (CH 2Cl 2)=1∶1] solvent was studied by UV Vis spectroscopic method, which indicated 1∶1 complexing between H 2HAPP and Zn(II) ion occurred easily in such a homogeneous system at room temperature. And the formation of ZnHAPP complex was further confirmed by FAB MS and 1H NMR spectra.展开更多
The development of routes and strategies for the design and preparation of complexes of 4d metals in moderate oxidation states is of great importance in magnetochemistry, bioinorganic chemistry, materials chemistry an...The development of routes and strategies for the design and preparation of complexes of 4d metals in moderate oxidation states is of great importance in magnetochemistry, bioinorganic chemistry, materials chemistry and solid-state chemistry. Bidentate ligands containing N or O donors especially phenanthroline have been widely used to form complexes with interesting structural motif. Reaction of M（CO）6 （M = Cr, Mo, W） with phenanthroline has been done in 1935 and produced an interesting stereo structure, but the reaction of MoOE（acac）2 （acac = acetylacetonato） with phenanthroline has not been studied yet. So, in this research, first of all MoOE（acac） 2 was prepared, and then it reacted with bidentate nitrogen donor to lead to produce the complex of [MoOEL2] （L = Phen） and different aspects of this complex were studied. This complex is very active and highly selective epoxidation catalyst. The structure of the product was characterized by various spectral techniques such as elemental analysis, IH NMR, 13C NMR and IR spectroscopy.展开更多
To design novel phenanthroline-derived soft ligands for selectively separating minor actinides from lanthanides, four tetradentate phenanthroline-derived heterocyclic ligands(BTPhen, BPyPhen, BPzPhen, and BBizPhen) we...To design novel phenanthroline-derived soft ligands for selectively separating minor actinides from lanthanides, four tetradentate phenanthroline-derived heterocyclic ligands(BTPhen, BPyPhen, BPzPhen, and BBizPhen) were constructed and their complexation behaviors with Am(ⅡI) and Eu(ⅡI) were systematically investigated by density functional theory(DFT) coupled with relativistic small-core pseudopotential. In all the 1:1-type species, the metal ion is in the center of the cavity and coordinates with two nitrogen atoms(N1 and N1′) of the phenanthroline skeleton and the other two nitrogen atoms(N2 and N2′) of the auxiliary groups. The bond lengths of Am–N are comparable to or even shorter than those of Eu–N bonds because the ionic radii of Am(ⅡI) are larger than those of Eu(ⅡI). Additionally, the negative ΔΔGAm/Eu value for the reaction of [M(H2O)4-(NO3)3] + L → ML(NO3)3 + 4H2 O indicates that the complexation reaction of Am(ⅡI) is more energetically favorable than that of Eu(ⅡI); this can be considered as an important design criterion to screen phenanthroline-derived ligands for MA(ⅡI) extraction. According to this criterion, the selectivity of tetradentate phenanthroline-derived ligands for separating Am(ⅡI) over Eu(ⅡI) follows the order of BTPhen > BBizPhen > BPyPhen > BPzPhen.展开更多
文摘Homogeneous solution of poor soluble aza bridged bis phenanthroline macrocyclic compound(H 2HAPP) was obtained by adding K 2CO 3 to its trifluoroacetate in CH 3OH CH 2Cl 2[ V (CH 3OH)∶ V (CH 2Cl 2)= 1∶1] solution. Coordination reaction between H 2HAPP and metal ion Zn(Ⅱ) in CH 3OH CH 2Cl 2[ V (CH 3OH)∶ V (CH 2Cl 2)=1∶1] solvent was studied by UV Vis spectroscopic method, which indicated 1∶1 complexing between H 2HAPP and Zn(II) ion occurred easily in such a homogeneous system at room temperature. And the formation of ZnHAPP complex was further confirmed by FAB MS and 1H NMR spectra.
文摘The development of routes and strategies for the design and preparation of complexes of 4d metals in moderate oxidation states is of great importance in magnetochemistry, bioinorganic chemistry, materials chemistry and solid-state chemistry. Bidentate ligands containing N or O donors especially phenanthroline have been widely used to form complexes with interesting structural motif. Reaction of M（CO）6 （M = Cr, Mo, W） with phenanthroline has been done in 1935 and produced an interesting stereo structure, but the reaction of MoOE（acac）2 （acac = acetylacetonato） with phenanthroline has not been studied yet. So, in this research, first of all MoOE（acac） 2 was prepared, and then it reacted with bidentate nitrogen donor to lead to produce the complex of [MoOEL2] （L = Phen） and different aspects of this complex were studied. This complex is very active and highly selective epoxidation catalyst. The structure of the product was characterized by various spectral techniques such as elemental analysis, IH NMR, 13C NMR and IR spectroscopy.
基金supported by the Major Research Plan"Breeding and Transmutation of Nuclear Fuel in Advanced Nuclear Fission Energy System"of the National Natural Science Foundation of China(91326202,91126006)the National Natural Science Foundation of China(21201166,11275219,11105162,21261140335)+1 种基金the"Strategic Priority Research Program"of the Chinese Academy of Sciences(XDA030104)the China Postdoctoral Science Foundation(2013M530734)
文摘To design novel phenanthroline-derived soft ligands for selectively separating minor actinides from lanthanides, four tetradentate phenanthroline-derived heterocyclic ligands(BTPhen, BPyPhen, BPzPhen, and BBizPhen) were constructed and their complexation behaviors with Am(ⅡI) and Eu(ⅡI) were systematically investigated by density functional theory(DFT) coupled with relativistic small-core pseudopotential. In all the 1:1-type species, the metal ion is in the center of the cavity and coordinates with two nitrogen atoms(N1 and N1′) of the phenanthroline skeleton and the other two nitrogen atoms(N2 and N2′) of the auxiliary groups. The bond lengths of Am–N are comparable to or even shorter than those of Eu–N bonds because the ionic radii of Am(ⅡI) are larger than those of Eu(ⅡI). Additionally, the negative ΔΔGAm/Eu value for the reaction of [M(H2O)4-(NO3)3] + L → ML(NO3)3 + 4H2 O indicates that the complexation reaction of Am(ⅡI) is more energetically favorable than that of Eu(ⅡI); this can be considered as an important design criterion to screen phenanthroline-derived ligands for MA(ⅡI) extraction. According to this criterion, the selectivity of tetradentate phenanthroline-derived ligands for separating Am(ⅡI) over Eu(ⅡI) follows the order of BTPhen > BBizPhen > BPyPhen > BPzPhen.
