The synthesis of organolanthanide compounds identified as LnCp^＊（MS）2PzA, Ln = Sm, Tb, Yb （MS = methanesulfonate, Cp^＊ = pentamethylcyclopentadienyl, and PzA = pyrazinamide）, by the reaction of coordination comp...The synthesis of organolanthanide compounds identified as LnCp^＊（MS）2PzA, Ln = Sm, Tb, Yb （MS = methanesulfonate, Cp^＊ = pentamethylcyclopentadienyl, and PzA = pyrazinamide）, by the reaction of coordination compounds Ln（MS）3（PzA）4 with NaCp in THF was reported. The complexes were formulated according to elemental analyses, complexometric titration with EDTA （%Ln）, and ^1H NMR. IR spectroscopy revealed that PzA coordinates with lanthanide （Ⅲ） ions and methanesulfonate coordinates via oxygen atoms in a non-equivalent manner. In preliminary catalytic studies, these compounds were active in styrene polymerization that used MAO as a cocatalyst with an activity of 12.3 kg PS molSm^-1h^-1. Differential scanning calorimetry （DSC） of polystyrene showed that the polymer was mainly atactic.展开更多
The title complex [CpIr{N（Ph2PS）2}（N3）]（N（Ph2PS）2=bis（diphenylthiophosphoryl）amide,Cp=pentamethylcyclopentadienyl） has been prepared and characterized by X-ray diffraction analysis.It crystallizes in monocli...The title complex [CpIr{N（Ph2PS）2}（N3）]（N（Ph2PS）2=bis（diphenylthiophosphoryl）amide,Cp=pentamethylcyclopentadienyl） has been prepared and characterized by X-ray diffraction analysis.It crystallizes in monoclinic,space group P21/n with a=11.6946（1）,b=18.9273（2）,c=15.7859（1）,β=105.731（1）°,V=3363.29（5）3,Z=4,Mr=817.92,Dc=1.615g/cm3,μ（MoKα）=4.219 mm-1,F（000）=1624,S=1.028,the final R=0.0355 and wR=0.0848 for 5987 observed reflections with Ⅰ〉2σ（Ⅰ） and 363 variables.The molecular structure of 1 consists of discrete monomeric molecule with a distorted octahedral configuration around the iridium atom, having a Cp^＊ ring at one face and bonded with a chelating bis（diphenylthiophosphoryl）amide group as well as a terminal azido ligand. The average Ir-S and Ir-N bond lengths are 2.416（1） and 2.121 （5） A, respectively.展开更多
Complexes of rare-earth-transition elements containing metal-metal bonds probably have potential catalytic properties and thus are important in theoretical research. Up to now, whether a metal-metal bond exists betwee...Complexes of rare-earth-transition elements containing metal-metal bonds probably have potential catalytic properties and thus are important in theoretical research. Up to now, whether a metal-metal bond exists between rare-earth and transition elements in these complexes is still a problem under discussion. In reports with data of structure determina-展开更多
基金Project supported by the Fundacā de Amparo à Pesquisa do Estado de Sāo Paulo and CNPq Conselho Nacional de Desenvolvimento Científico e Teenológico
文摘The synthesis of organolanthanide compounds identified as LnCp^＊（MS）2PzA, Ln = Sm, Tb, Yb （MS = methanesulfonate, Cp^＊ = pentamethylcyclopentadienyl, and PzA = pyrazinamide）, by the reaction of coordination compounds Ln（MS）3（PzA）4 with NaCp in THF was reported. The complexes were formulated according to elemental analyses, complexometric titration with EDTA （%Ln）, and ^1H NMR. IR spectroscopy revealed that PzA coordinates with lanthanide （Ⅲ） ions and methanesulfonate coordinates via oxygen atoms in a non-equivalent manner. In preliminary catalytic studies, these compounds were active in styrene polymerization that used MAO as a cocatalyst with an activity of 12.3 kg PS molSm^-1h^-1. Differential scanning calorimetry （DSC） of polystyrene showed that the polymer was mainly atactic.
基金supported by the National Natural Science Foundation of Chinathe Program for New Century Excellent Talents in University (20771003 and NCET-06-0556)
文摘The title complex [CpIr{N（Ph2PS）2}（N3）]（N（Ph2PS）2=bis（diphenylthiophosphoryl）amide,Cp=pentamethylcyclopentadienyl） has been prepared and characterized by X-ray diffraction analysis.It crystallizes in monoclinic,space group P21/n with a=11.6946（1）,b=18.9273（2）,c=15.7859（1）,β=105.731（1）°,V=3363.29（5）3,Z=4,Mr=817.92,Dc=1.615g/cm3,μ（MoKα）=4.219 mm-1,F（000）=1624,S=1.028,the final R=0.0355 and wR=0.0848 for 5987 observed reflections with Ⅰ〉2σ（Ⅰ） and 363 variables.The molecular structure of 1 consists of discrete monomeric molecule with a distorted octahedral configuration around the iridium atom, having a Cp^＊ ring at one face and bonded with a chelating bis（diphenylthiophosphoryl）amide group as well as a terminal azido ligand. The average Ir-S and Ir-N bond lengths are 2.416（1） and 2.121 （5） A, respectively.
基金Project supported by the National Natural Science Foundation of China
文摘Complexes of rare-earth-transition elements containing metal-metal bonds probably have potential catalytic properties and thus are important in theoretical research. Up to now, whether a metal-metal bond exists between rare-earth and transition elements in these complexes is still a problem under discussion. In reports with data of structure determina-
