Polymer-supported bimetallic system of PdCl2-4NiCl2-PPH3/PVP [PVP= poly(N-vinyl-2-pyrrolidone)] provided an almost regiospecific conversion of styrene to thebranched methyl 2-propionate at a high conversion. Typical r...Polymer-supported bimetallic system of PdCl2-4NiCl2-PPH3/PVP [PVP= poly(N-vinyl-2-pyrrolidone)] provided an almost regiospecific conversion of styrene to thebranched methyl 2-propionate at a high conversion. Typical reaction conditions are: 353 K,2.1 MPa of CO pressure (gauge pressure), 10h; styrene (1 mmol); methanol (0. 8 mL) ;benzene (10 mL); PdCl2/PVP(0. 04 mmol Pd, N/Pd= 20 in molar ratio); n (Pd): n(Ni): n(PPh3) = 1: 4:1. A remarkable synergic effect of bimetallic catalyst can be observed.Effects of PVP, amount of triphenylphosphine and temperature on the reaction were studied.The system of PdCl2-4NiCl2-PPh3/PVP gave 100% conversion of styrene and 99% selectivityto the branched chain ester under the typical reaction conditions.展开更多
The fullerene complexes, η2-C70[RhCl（CO）（PPh3）2]n（n=1, 2）, have been prepared by the reaction of C70 with RhCl（CO）（PPh3）2 in methylbenzene at room temperature. The new complexes were characterized by UV-Vis...The fullerene complexes, η2-C70[RhCl（CO）（PPh3）2]n（n=1, 2）, have been prepared by the reaction of C70 with RhCl（CO）（PPh3）2 in methylbenzene at room temperature. The new complexes were characterized by UV-Vis spectra, IR, XPS and elemental analysis. The results show that the complexes of η2 form can be formed by RhCl（CO）（PPh3）2 bonding to C70 in theσ-π way. In addition, the complexes structures have been supposed.展开更多
'Living'/controlled radical polymerization of ethyl methacrylate (EMA) was carried out with a 2,2'-azobisisobutyronitrile (AIBN)/ferric chloride (FeCl_3)/triphenylphosphine (PPh_3) initiation system at 85...'Living'/controlled radical polymerization of ethyl methacrylate (EMA) was carried out with a 2,2'-azobisisobutyronitrile (AIBN)/ferric chloride (FeCl_3)/triphenylphosphine (PPh_3) initiation system at 85℃. Thc numberaverage molecular weight (M_n) increases linearly with monomer conversion and the rate of polymerization is first order withrespect to monomer concentration. The M_w of PEMA ranges from 3900 to 17600 and the polydispersity indices are quitenarrow (1.09～1.22). The conversion can reach up to～100% and M_w of the polymers obtained is close to that designed. Thepolymerization mechanism belongs to the reverse atom transfer radical polymerization (ATRP). The polymer was end-functionalized by chlorine atom, which acts as a macroinitiator to proceed extension polymerization in the presence ofCuBr/bipy catalyst system via an ATRP process. The presence of ω-chlorine in the PEMA obtained was identified by ~1H-NMR spectrum.展开更多
A 60%Fe/Al_2O_3 catalyst was prepared by the co-precipitation method.It was reduced by H_2 to produce metallic Fe,which was then sulfided by CS_2 to Fe_(0.96) S and Fe_3S_4 or phosphided by triphenylphosphine(PPh3) in...A 60%Fe/Al_2O_3 catalyst was prepared by the co-precipitation method.It was reduced by H_2 to produce metallic Fe,which was then sulfided by CS_2 to Fe_(0.96) S and Fe_3S_4 or phosphided by triphenylphosphine(PPh3) in liquid phases to Fe2 P and Fe P.It was found that the iron sulfides(Fe0.96 S and Fe_3S_4) exhibited the low activity for the hydrodesulfurization(HDS) reactions.The HDS activity was also low on the Fe(metal)/Al_2O_3 and Fe_2 P/Al_2O_3 catalysts since they were converted into Fe0.96 S and Fe_3S_4 during the HDS reactions.In contrast,the FeP/Al_2O_3 was found to be stable and active for the HDS reactions.In particular,Fe P/Al_2O_3 possessed significantly smaller Fe P particles than Fe P/C,leading to the significant higher HDS activity of FeP/Al_2O_3 than Fe P/C.展开更多
文摘Polymer-supported bimetallic system of PdCl2-4NiCl2-PPH3/PVP [PVP= poly(N-vinyl-2-pyrrolidone)] provided an almost regiospecific conversion of styrene to thebranched methyl 2-propionate at a high conversion. Typical reaction conditions are: 353 K,2.1 MPa of CO pressure (gauge pressure), 10h; styrene (1 mmol); methanol (0. 8 mL) ;benzene (10 mL); PdCl2/PVP(0. 04 mmol Pd, N/Pd= 20 in molar ratio); n (Pd): n(Ni): n(PPh3) = 1: 4:1. A remarkable synergic effect of bimetallic catalyst can be observed.Effects of PVP, amount of triphenylphosphine and temperature on the reaction were studied.The system of PdCl2-4NiCl2-PPh3/PVP gave 100% conversion of styrene and 99% selectivityto the branched chain ester under the typical reaction conditions.
文摘The fullerene complexes, η2-C70[RhCl（CO）（PPh3）2]n（n=1, 2）, have been prepared by the reaction of C70 with RhCl（CO）（PPh3）2 in methylbenzene at room temperature. The new complexes were characterized by UV-Vis spectra, IR, XPS and elemental analysis. The results show that the complexes of η2 form can be formed by RhCl（CO）（PPh3）2 bonding to C70 in theσ-π way. In addition, the complexes structures have been supposed.
文摘'Living'/controlled radical polymerization of ethyl methacrylate (EMA) was carried out with a 2,2'-azobisisobutyronitrile (AIBN)/ferric chloride (FeCl_3)/triphenylphosphine (PPh_3) initiation system at 85℃. Thc numberaverage molecular weight (M_n) increases linearly with monomer conversion and the rate of polymerization is first order withrespect to monomer concentration. The M_w of PEMA ranges from 3900 to 17600 and the polydispersity indices are quitenarrow (1.09～1.22). The conversion can reach up to～100% and M_w of the polymers obtained is close to that designed. Thepolymerization mechanism belongs to the reverse atom transfer radical polymerization (ATRP). The polymer was end-functionalized by chlorine atom, which acts as a macroinitiator to proceed extension polymerization in the presence ofCuBr/bipy catalyst system via an ATRP process. The presence of ω-chlorine in the PEMA obtained was identified by ~1H-NMR spectrum.
基金Financial supports from the NSFC-DFG (21761132006),NSFC (21773108)fundamental research funds for central universities are acknowledged
文摘A 60%Fe/Al_2O_3 catalyst was prepared by the co-precipitation method.It was reduced by H_2 to produce metallic Fe,which was then sulfided by CS_2 to Fe_(0.96) S and Fe_3S_4 or phosphided by triphenylphosphine(PPh3) in liquid phases to Fe2 P and Fe P.It was found that the iron sulfides(Fe0.96 S and Fe_3S_4) exhibited the low activity for the hydrodesulfurization(HDS) reactions.The HDS activity was also low on the Fe(metal)/Al_2O_3 and Fe_2 P/Al_2O_3 catalysts since they were converted into Fe0.96 S and Fe_3S_4 during the HDS reactions.In contrast,the FeP/Al_2O_3 was found to be stable and active for the HDS reactions.In particular,Fe P/Al_2O_3 possessed significantly smaller Fe P particles than Fe P/C,leading to the significant higher HDS activity of FeP/Al_2O_3 than Fe P/C.
