Complexes of La(Ⅲ),Nd(Ⅲ),Sm(Ⅲ),Eu(Ⅲ),Gd(Ⅲ),Dy(Ⅲ), Er(Ⅲ),Yb(Ⅲ)and Y(Ⅲ)with piperonal isonicotinoyl hydrazone(HPIN) have been synthesized in DMF and EtOH.The complexes have been characte- rized by elemental ana...Complexes of La(Ⅲ),Nd(Ⅲ),Sm(Ⅲ),Eu(Ⅲ),Gd(Ⅲ),Dy(Ⅲ), Er(Ⅲ),Yb(Ⅲ)and Y(Ⅲ)with piperonal isonicotinoyl hydrazone(HPIN) have been synthesized in DMF and EtOH.The complexes have been characte- rized by elemental analysis,molar conductance,i.r.,UV and^1H n.m.r. spectra,magnetic measurements,X-ray powder diffraction and DTA.展开更多
The syndiotactic polymerization of styrene（St） and the copolymerization of St with ethylene（E） were carried out by using a series of chiral half-sandwich rare-earth metal dialkyl complexes（Cp^x＊） as the catalys...The syndiotactic polymerization of styrene（St） and the copolymerization of St with ethylene（E） were carried out by using a series of chiral half-sandwich rare-earth metal dialkyl complexes（Cp^x＊） as the catalysts. The complexes are Ln（CH2SiMe3）2（THF）（1-4： Ln = Sc（1）, Ln = Lu（2）, Ln = Y（3）, Ln = Dy（4）） bearing chiral cyclopentadienyl ligand containing bulky cylcohexane derivatives in the presence of activator and AliBu3. For the St polymerization, a high activity up to 3.1 × 10^6 g of polymer mol Ln^-1·h^-1 and a high syndiotactic selectivity more than 99% were achieved. The resulting syndiotactic polystyrenes（sPSs） have the molecular weights（Mn） ranging from 3700 g·mol^-1 to 6400 g·mol^-1 and the molecular weight distributions（Mw/Mn） from 1.40 to 5.03. As for the copolymerization of St and E, the activity was up to 2.4 × 10^6 g of copolymer mol Sc^-1·h^-1·MPa^-1, giving random St-E copolymers containing syndiotactic polystyrene sequences with different St content in the range of 15 mol%-58 mol%. These results demonstrate that the bulky cyclopentadienyl ligands of the chiral half-sandwich rare-earth metal complexes effectively inhibit the continued insertion of St monomers into the（co）polymer chain to some extent in comparison with the known half-sandwich rare-earth metal complexes.展开更多
Eleven homobinuclear macrocyclic rare earth metal ions complexes are obtained as com-pounds of 2:2 Schiff base formed by condensing 2,6-diformyl-4-tert-Butylphenol and triethy-lenetetramine by a template procedure usi...Eleven homobinuclear macrocyclic rare earth metal ions complexes are obtained as com-pounds of 2:2 Schiff base formed by condensing 2,6-diformyl-4-tert-Butylphenol and triethy-lenetetramine by a template procedure using rare earth metal isothiocyanates. These complexesare characterized by elemental analyses, FABMS, IR, conductivity and magnetic susceptibility.The variable-temperature magnetic susceptibility (4--300K) of complexes of Gd(Ⅲ) and Tb(Ⅲ) has been determined. A satisfactory fit to theoretical curve derived from spin Hamil-tonian operator was obtained by least squares method. The exchange interaction parameters areJ =-0.220 cm^(-1) for Gd, ,ZJ~?=-0.052 cm^(-1) for Tb. The results indicate a very weak anti-ferromagnetic interaction between Gd^(3+)-Gd^(3+), Tb^(3+)-Tb^(3+) ions.展开更多
Ternary inclusion complexes β-cyclodextrin （β-CD）, rare earth metal ions （YbC13, YC13）, and 1,8-naphthalene- diamine/ 1,5-naphthalenediamine are synthesized in basic aqueous media, which are characterized via IH...Ternary inclusion complexes β-cyclodextrin （β-CD）, rare earth metal ions （YbC13, YC13）, and 1,8-naphthalene- diamine/ 1,5-naphthalenediamine are synthesized in basic aqueous media, which are characterized via IH NMR and IR spectroscopy. The stoichiometric proportion of β-CD ： YbC13 ： 1, 5-naphthalenedia- mine is 2：1：2, that of β-CD：YCI3 ： 1,8-naphthalenediamine is 2：1：1, and that of β-CD：YbC13 ： 1,8-naphthalenediamine is 2 ： 1 ： 1. The IR spectroscopy of the ternary inclusion complexes in the range of 935-1 000 cm 1 reveals the existence of the coordinate bond M---O or M---N. The possible conformations of the ternary inclusion complexes are depicted.展开更多
The reactivities of benzoxazine functionalized amine bridged bis(phenol)s LnH_(2)(n=1—3)with rare earth metal complexes were explored,founding that both the aryl substituents of the ligand and the rare earth metals h...The reactivities of benzoxazine functionalized amine bridged bis(phenol)s LnH_(2)(n=1—3)with rare earth metal complexes were explored,founding that both the aryl substituents of the ligand and the rare earth metals have profound influences on reaction outcomes.展开更多
Three new metal complexes derived from Er（Ⅲ）, Dy（Ⅲ） and Zr（Ⅳ） with 2-aminobenzohydrazide （ABH） were synthesized and characterized by elemental analyses, IR, ^1H-NMR, ES-MS and transmission electron microsco...Three new metal complexes derived from Er（Ⅲ）, Dy（Ⅲ） and Zr（Ⅳ） with 2-aminobenzohydrazide （ABH） were synthesized and characterized by elemental analyses, IR, ^1H-NMR, ES-MS and transmission electron microscopy （TEM）. The morphology and the particle size were determined by TEM. The results showed that the ligand acted as neutral bi-dentate coordinating to the metal ions through the carbonyl oxygen and amidic amino nitrogen. The aromatic amine group remained inert towards coordination. The optical band gap was measured and found to be 3.3, 3.5 and 4.3 eV for Er（Ⅲ）, Dy（Ⅲ） and Zr（Ⅳ）, respectively. The optical band gap values indicated a semi-conducting nature of the investigated complexes. The anti-inflammatory and analgesic activities of the tested compounds were determined and compared with standard meloxicam.展开更多
This paper gives a brief overview on recent progress in the chemistry of rare-earth dialkyl and dihydride complexes with monoanionic supporting ligands.The dialkyl complexes serve as excellent catalysts for the polyme...This paper gives a brief overview on recent progress in the chemistry of rare-earth dialkyl and dihydride complexes with monoanionic supporting ligands.The dialkyl complexes serve as excellent catalysts for the polymerization and copolymerization of a wide range of olefins to give novel polymer materials difficult to prepare by other means.The dihydride species show unique features in terms of both their structure and reactivity,which are in sharp contrast with those of the monohydride analogues bearing two supporting ligands.展开更多
文摘Complexes of La(Ⅲ),Nd(Ⅲ),Sm(Ⅲ),Eu(Ⅲ),Gd(Ⅲ),Dy(Ⅲ), Er(Ⅲ),Yb(Ⅲ)and Y(Ⅲ)with piperonal isonicotinoyl hydrazone(HPIN) have been synthesized in DMF and EtOH.The complexes have been characte- rized by elemental analysis,molar conductance,i.r.,UV and^1H n.m.r. spectra,magnetic measurements,X-ray powder diffraction and DTA.
基金financially supported by the National Natural Science Foundation of China (Nos. 20974014, 21274012, 21322401 and 21774014)the 111 project (No. B07012)
文摘The syndiotactic polymerization of styrene（St） and the copolymerization of St with ethylene（E） were carried out by using a series of chiral half-sandwich rare-earth metal dialkyl complexes（Cp^x＊） as the catalysts. The complexes are Ln（CH2SiMe3）2（THF）（1-4： Ln = Sc（1）, Ln = Lu（2）, Ln = Y（3）, Ln = Dy（4）） bearing chiral cyclopentadienyl ligand containing bulky cylcohexane derivatives in the presence of activator and AliBu3. For the St polymerization, a high activity up to 3.1 × 10^6 g of polymer mol Ln^-1·h^-1 and a high syndiotactic selectivity more than 99% were achieved. The resulting syndiotactic polystyrenes（sPSs） have the molecular weights（Mn） ranging from 3700 g·mol^-1 to 6400 g·mol^-1 and the molecular weight distributions（Mw/Mn） from 1.40 to 5.03. As for the copolymerization of St and E, the activity was up to 2.4 × 10^6 g of copolymer mol Sc^-1·h^-1·MPa^-1, giving random St-E copolymers containing syndiotactic polystyrene sequences with different St content in the range of 15 mol%-58 mol%. These results demonstrate that the bulky cyclopentadienyl ligands of the chiral half-sandwich rare-earth metal complexes effectively inhibit the continued insertion of St monomers into the（co）polymer chain to some extent in comparison with the known half-sandwich rare-earth metal complexes.
基金Project supported by the National Natural Science Foundation of China.
文摘Eleven homobinuclear macrocyclic rare earth metal ions complexes are obtained as com-pounds of 2:2 Schiff base formed by condensing 2,6-diformyl-4-tert-Butylphenol and triethy-lenetetramine by a template procedure using rare earth metal isothiocyanates. These complexesare characterized by elemental analyses, FABMS, IR, conductivity and magnetic susceptibility.The variable-temperature magnetic susceptibility (4--300K) of complexes of Gd(Ⅲ) and Tb(Ⅲ) has been determined. A satisfactory fit to theoretical curve derived from spin Hamil-tonian operator was obtained by least squares method. The exchange interaction parameters areJ =-0.220 cm^(-1) for Gd, ,ZJ~?=-0.052 cm^(-1) for Tb. The results indicate a very weak anti-ferromagnetic interaction between Gd^(3+)-Gd^(3+), Tb^(3+)-Tb^(3+) ions.
基金Supported by the Project of Education Department of Liaoning Province (20040084)
文摘Ternary inclusion complexes β-cyclodextrin （β-CD）, rare earth metal ions （YbC13, YC13）, and 1,8-naphthalene- diamine/ 1,5-naphthalenediamine are synthesized in basic aqueous media, which are characterized via IH NMR and IR spectroscopy. The stoichiometric proportion of β-CD ： YbC13 ： 1, 5-naphthalenedia- mine is 2：1：2, that of β-CD：YCI3 ： 1,8-naphthalenediamine is 2：1：1, and that of β-CD：YbC13 ： 1,8-naphthalenediamine is 2 ： 1 ： 1. The IR spectroscopy of the ternary inclusion complexes in the range of 935-1 000 cm 1 reveals the existence of the coordinate bond M---O or M---N. The possible conformations of the ternary inclusion complexes are depicted.
基金support fromtheNational Natural Science Foundation of China(21871198)the Major Research Project of the Natural Science of the Jiangsu Higher Education Institutions(19KJA360005),and PAPD.
文摘The reactivities of benzoxazine functionalized amine bridged bis(phenol)s LnH_(2)(n=1—3)with rare earth metal complexes were explored,founding that both the aryl substituents of the ligand and the rare earth metals have profound influences on reaction outcomes.
文摘Three new metal complexes derived from Er（Ⅲ）, Dy（Ⅲ） and Zr（Ⅳ） with 2-aminobenzohydrazide （ABH） were synthesized and characterized by elemental analyses, IR, ^1H-NMR, ES-MS and transmission electron microscopy （TEM）. The morphology and the particle size were determined by TEM. The results showed that the ligand acted as neutral bi-dentate coordinating to the metal ions through the carbonyl oxygen and amidic amino nitrogen. The aromatic amine group remained inert towards coordination. The optical band gap was measured and found to be 3.3, 3.5 and 4.3 eV for Er（Ⅲ）, Dy（Ⅲ） and Zr（Ⅳ）, respectively. The optical band gap values indicated a semi-conducting nature of the investigated complexes. The anti-inflammatory and analgesic activities of the tested compounds were determined and compared with standard meloxicam.
文摘This paper gives a brief overview on recent progress in the chemistry of rare-earth dialkyl and dihydride complexes with monoanionic supporting ligands.The dialkyl complexes serve as excellent catalysts for the polymerization and copolymerization of a wide range of olefins to give novel polymer materials difficult to prepare by other means.The dihydride species show unique features in terms of both their structure and reactivity,which are in sharp contrast with those of the monohydride analogues bearing two supporting ligands.
