A new type of selenious polymer, silica-bound polybispropoxyethyl-selenidesilsesquinoxane, and its platinum complex were synthesized from bis-allyloxyethyl selenide via hydrosilylation with triethoxysilane, followed b...A new type of selenious polymer, silica-bound polybispropoxyethyl-selenidesilsesquinoxane, and its platinum complex were synthesized from bis-allyloxyethyl selenide via hydrosilylation with triethoxysilane, followed by immobilized on fumed silica, and then reacting with potassium chloroplatinite under nitrogen atmosphere in acetone. It was found that the platinum complex can catalyze the hydrosilylation of olefins with triethoxysilane effectively. The effects of the nature of the substrate, the amount of complex used, and the reaction temperature on the catalytic activity were investigated.展开更多
The hydrosilylation of alkenes with triethoxysilane has been achieved at 120 C in the presence of 0.01 mol%of thioetherfunctionalized MCM-41 anchored rhodium complex,affording the corresponding addition products in 68...The hydrosilylation of alkenes with triethoxysilane has been achieved at 120 C in the presence of 0.01 mol%of thioetherfunctionalized MCM-41 anchored rhodium complex,affording the corresponding addition products in 68-91%yields.This supported rhodium complex can be reused several times without noticeable loss of activity.Our system not only solves the basic problems of catalyst separation and recovery,but also avoids the use of phosphine ligands.展开更多
In the framework of density functional theory （DFT）, we have studied the electronic properties of alkene/alkyne- hydrosilylated silicon nanocrystals （Si NCs） in the size range from 0.8 nm to 1.6 nm. Among the alke...In the framework of density functional theory （DFT）, we have studied the electronic properties of alkene/alkyne- hydrosilylated silicon nanocrystals （Si NCs） in the size range from 0.8 nm to 1.6 nm. Among the alkenes with all kinds of functional groups considered in this work, only those containing -NH2 and -C4H3S lead to significant hydrosilylation- induced changes in the gap between the highest occupied molecular orbital （HOMO） and the lowest unoccupied molecular orbital （LUMO） of an Si NC at the ground state. The quantum confinement effect is dominant for all of the alkene- hydrosilylated Si NCs at the ground state. At the excited state, the prevailing effect of surface chemistry only occurs at the smallest （0.8 nm） Si NCs hydrosilylated with alkenes containing -NH2 and -C4H3S. Although the alkyne hydrosilylation gives rise to a more significant surface chemistry effect than alkene hydrosilylation, the quantum confinement effect remains dominant for alkyne-hydrosilylated Si NCs at the ground state. However, at the excited state, the effect of surface chemistry induced by the hydrosilylation with conjugated alkynes is strong enough to prevail over that of quantum confinement.展开更多
The hydrosilylation reaction of ladderlike polyvinylsilsesquioxane (Vi-T) with 1, 1, 3, 3-tetramethyldisiloxane (H-MM) catalyzed by dicyclopentadienyl-dichloroplatinium (Cp2PtCl2) was carried out well in tetrahydrofur...The hydrosilylation reaction of ladderlike polyvinylsilsesquioxane (Vi-T) with 1, 1, 3, 3-tetramethyldisiloxane (H-MM) catalyzed by dicyclopentadienyl-dichloroplatinium (Cp2PtCl2) was carried out well in tetrahydrofuran (THF) to produce a soluble white solid. This product was characterized by IR, H-1-NMR, C-13-NMR, Si-29-NMR, DSC, X-ray diffraction method, gel permeation chromatography (GPC), vapour pressure osmometry (VPO), atomic force microscopy (AFM) and molecular simulation. These results prove that the product contains nanoscale tubular structure.展开更多
Silica-bound mercaptoselenaether-containing silsesquioxane and its platinum or rhodium complex were synthesized from gamma-(2,3-epithiopropyl) propyltrimethoxysilane via ring-opening reaction with bis(2-hydroxyethyl) ...Silica-bound mercaptoselenaether-containing silsesquioxane and its platinum or rhodium complex were synthesized from gamma-(2,3-epithiopropyl) propyltrimethoxysilane via ring-opening reaction with bis(2-hydroxyethyl) selenide, followed by hydrolysis and immobilization on fumed silica, and then reacting with potassium chloroplatinite or rhodium chloride in acetone under nitrogen atmosphere. It was found that two noble metal complexes can catalyze the hydrosilylation of olefins with triethoxysilane effectively. The influences of temperature, the amount of complex used, the nature of olefin on catalytic activity were investigated.展开更多
5,11,17,23-Tetrakis-1′, 1′-dimethylethyl-25,27-dihydroxy-26,28-1″, 7″, 13″-trioxa-4″, 10″-dithiatridecylcene-calix[4]arene (calix[4]dithiacrown-5) and its O-methylated derivate (dimethylcalix[4]dithiacrown-5) w...5,11,17,23-Tetrakis-1′, 1′-dimethylethyl-25,27-dihydroxy-26,28-1″, 7″, 13″-trioxa-4″, 10″-dithiatridecylcene-calix[4]arene (calix[4]dithiacrown-5) and its O-methylated derivate (dimethylcalix[4]dithiacrown-5) were synthesized fromp-tert-butylcalix[4] arene via 1, 3-lower rim functionalization with chloroethyltosylate, followed by ring-closing condensation with β,β/t'-dimercaptoethyl ether in the presence of sodium ethoxide as a base in reflux ethanol under nitrogen atmosphere, followed by methylation with methyltosylate in the presence of NaH as a base in dioxane. It was found that they can coordinate with platinous chloride and the platinous complexes are efficient catalysts for the hydrosilylation of olefins with triethoxysilane.展开更多
A modified method of preparing crown functionalized linear polysiloxane has been described.4'-allylbenzo-15-crown-5 was subjected to hydrosilylation with methyldichlorosilane,followed bypolycondensation with silan...A modified method of preparing crown functionalized linear polysiloxane has been described.4'-allylbenzo-15-crown-5 was subjected to hydrosilylation with methyldichlorosilane,followed bypolycondensation with silanol-terminated polydimethylsiloxane to give the title crownfunctionalized linear polysiloxane. It was found that the polysiloxane could be coordinated withplatinum salt to form platinum complex, which could catalyze the hydrosilylation of olefins withtriethoxysilane efficiently.展开更多
Silica-bound 15-Crown-5, 18-Crown-6 with a spacer of propyloxymethyl and their platinum complexes have been synthesized. It was found that they were efficient catalysts for the hydrosilylation of olefms with triethoxy...Silica-bound 15-Crown-5, 18-Crown-6 with a spacer of propyloxymethyl and their platinum complexes have been synthesized. It was found that they were efficient catalysts for the hydrosilylation of olefms with triethoxysilane in the temperature range of 60 to 130 ℃.展开更多
Fullerene n propylamine platinum,rhodium complex have been prepared from C 60 via amination with n propylamine, then reacting respectively with potassium chloroplatinite or rhodium chloride. The two nob...Fullerene n propylamine platinum,rhodium complex have been prepared from C 60 via amination with n propylamine, then reacting respectively with potassium chloroplatinite or rhodium chloride. The two noble metal complexes can effectively catalyze hydrosilylation of olefins with triethoxysilane. The Pt complex exhibits high regioselectivty for styrene, nearly 100% branched product is obtained.展开更多
The synthesis of a new type of selena aza crown ether 6 (4 nitrobenzyl) 1,4,7,10 selenatriazacyclododecane (L) derivated from phenylalanine , and its platinum(Ⅱ) complex was described. The catalytic activity of...The synthesis of a new type of selena aza crown ether 6 (4 nitrobenzyl) 1,4,7,10 selenatriazacyclododecane (L) derivated from phenylalanine , and its platinum(Ⅱ) complex was described. The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.展开更多
An electrode development was needed with high efficiency and low costs as next generation solar cells. We attempted the electrode fabrication for a photoelectrochemical cell by immobilizing functional groups on a n-Si...An electrode development was needed with high efficiency and low costs as next generation solar cells. We attempted the electrode fabrication for a photoelectrochemical cell by immobilizing functional groups on a n-Si(111) surface. The immobilization was applied by hydrosilylation terminated with ester (hydrophobic) or carbonyl (hydrophilic) group. Results confirmed the immobilization on the Si surface by measuring ATR-FTIR and XPS.展开更多
The title complex (PtL_2Cl_2) was synthesized by reacting 10-selenabenzo-15-crown-5 (L) with potassium chloroplatinite. Its catalytic activity for the hydrosilylation of olefins by triethoxysilane, was investi gated.
The syntheses of a new type of heteromacrocyclic polyether- 2,3-benzo-1,4,7,13-tetraoxa-10-telluracyclopentadeca-2-ene(L),and its pla- tinum complex(PtL_2Cl_2)were described.The catalytic activity of this complex for ...The syntheses of a new type of heteromacrocyclic polyether- 2,3-benzo-1,4,7,13-tetraoxa-10-telluracyclopentadeca-2-ene(L),and its pla- tinum complex(PtL_2Cl_2)were described.The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.展开更多
Asymmetric hydrisilylation catalyzed by polymeric thiazolidine rhodium catalystswas conducted. Almost the same optical yields have been obtained when comb-shapedpolymeric ligands and their corresponding monomer comple...Asymmetric hydrisilylation catalyzed by polymeric thiazolidine rhodium catalystswas conducted. Almost the same optical yields have been obtained when comb-shapedpolymeric ligands and their corresponding monomer complexed rhodium cataltystswere used to asymmetric hydrosilylation of acetophenone. Optical yield of chira 1- methylbenzyl alcohol reaches as high as 71.5%. Temperature dependence of enantio- selective hydrosilylation of acetophenone was discussed.展开更多
With the increasing demand for homoallylic silanes and allylic silanes,the highly efficient and regioselective hydrosilylations of conjugated dienes are urgently needed.Herein,we developed a Ni-catalyzed regiodivergen...With the increasing demand for homoallylic silanes and allylic silanes,the highly efficient and regioselective hydrosilylations of conjugated dienes are urgently needed.Herein,we developed a Ni-catalyzed regiodivergent hydrosilylation of aromatic conjugated dienes by adjusting the temperature and ligands.Under low temperature(-30℃),an eternal-ligand-free system(Ni/t-BuOk)can efficiently facilitate the 3,4-anti-Markovnikov hydrosilylation to provide homoallylic silanes via electrophilic activation process;under room temperature(25℃),a ligand-controlled system(Ni/t-BuOk/PPh3)can eventuate the 3,4-Markovnikov hydrosilylation to produce allylic silanes via Chalk-Harrod process.Both systems are compatible with various conjugated dienes and primary silanes in excellent yields andregioselectivities.展开更多
文摘A new type of selenious polymer, silica-bound polybispropoxyethyl-selenidesilsesquinoxane, and its platinum complex were synthesized from bis-allyloxyethyl selenide via hydrosilylation with triethoxysilane, followed by immobilized on fumed silica, and then reacting with potassium chloroplatinite under nitrogen atmosphere in acetone. It was found that the platinum complex can catalyze the hydrosilylation of olefins with triethoxysilane effectively. The effects of the nature of the substrate, the amount of complex used, and the reaction temperature on the catalytic activity were investigated.
基金National Natural Science Foundation of China(No.20862008)Natural Science Foundation of Jiangxi Province(No.2008GQH0034) for financial support
文摘The hydrosilylation of alkenes with triethoxysilane has been achieved at 120 C in the presence of 0.01 mol%of thioetherfunctionalized MCM-41 anchored rhodium complex,affording the corresponding addition products in 68-91%yields.This supported rhodium complex can be reused several times without noticeable loss of activity.Our system not only solves the basic problems of catalyst separation and recovery,but also avoids the use of phosphine ligands.
基金supported by the National Basic Research Program of China(Grant No.2013CB632101)the National Natural Science Foundation of China forExcellent Young Researchers(Grant No.61222404)+1 种基金the Research and Development Program of Ministry of Education of China(Grant No.62501040202)the 2012 UAlberta MOST Joint Research Laboratories Program,China
文摘In the framework of density functional theory （DFT）, we have studied the electronic properties of alkene/alkyne- hydrosilylated silicon nanocrystals （Si NCs） in the size range from 0.8 nm to 1.6 nm. Among the alkenes with all kinds of functional groups considered in this work, only those containing -NH2 and -C4H3S lead to significant hydrosilylation- induced changes in the gap between the highest occupied molecular orbital （HOMO） and the lowest unoccupied molecular orbital （LUMO） of an Si NC at the ground state. The quantum confinement effect is dominant for all of the alkene- hydrosilylated Si NCs at the ground state. At the excited state, the prevailing effect of surface chemistry only occurs at the smallest （0.8 nm） Si NCs hydrosilylated with alkenes containing -NH2 and -C4H3S. Although the alkyne hydrosilylation gives rise to a more significant surface chemistry effect than alkene hydrosilylation, the quantum confinement effect remains dominant for alkyne-hydrosilylated Si NCs at the ground state. However, at the excited state, the effect of surface chemistry induced by the hydrosilylation with conjugated alkynes is strong enough to prevail over that of quantum confinement.
基金This project was supported by NSFC(59483001 & 29574187)& Chinese Academy of Sciences(KJ-952-S1-508)
文摘The hydrosilylation reaction of ladderlike polyvinylsilsesquioxane (Vi-T) with 1, 1, 3, 3-tetramethyldisiloxane (H-MM) catalyzed by dicyclopentadienyl-dichloroplatinium (Cp2PtCl2) was carried out well in tetrahydrofuran (THF) to produce a soluble white solid. This product was characterized by IR, H-1-NMR, C-13-NMR, Si-29-NMR, DSC, X-ray diffraction method, gel permeation chromatography (GPC), vapour pressure osmometry (VPO), atomic force microscopy (AFM) and molecular simulation. These results prove that the product contains nanoscale tubular structure.
文摘Silica-bound mercaptoselenaether-containing silsesquioxane and its platinum or rhodium complex were synthesized from gamma-(2,3-epithiopropyl) propyltrimethoxysilane via ring-opening reaction with bis(2-hydroxyethyl) selenide, followed by hydrolysis and immobilization on fumed silica, and then reacting with potassium chloroplatinite or rhodium chloride in acetone under nitrogen atmosphere. It was found that two noble metal complexes can catalyze the hydrosilylation of olefins with triethoxysilane effectively. The influences of temperature, the amount of complex used, the nature of olefin on catalytic activity were investigated.
文摘5,11,17,23-Tetrakis-1′, 1′-dimethylethyl-25,27-dihydroxy-26,28-1″, 7″, 13″-trioxa-4″, 10″-dithiatridecylcene-calix[4]arene (calix[4]dithiacrown-5) and its O-methylated derivate (dimethylcalix[4]dithiacrown-5) were synthesized fromp-tert-butylcalix[4] arene via 1, 3-lower rim functionalization with chloroethyltosylate, followed by ring-closing condensation with β,β/t'-dimercaptoethyl ether in the presence of sodium ethoxide as a base in reflux ethanol under nitrogen atmosphere, followed by methylation with methyltosylate in the presence of NaH as a base in dioxane. It was found that they can coordinate with platinous chloride and the platinous complexes are efficient catalysts for the hydrosilylation of olefins with triethoxysilane.
基金This work was supported by the National Natural Science Foundation of China and the Natural Science Foundation of Hubei Province
文摘A modified method of preparing crown functionalized linear polysiloxane has been described.4'-allylbenzo-15-crown-5 was subjected to hydrosilylation with methyldichlorosilane,followed bypolycondensation with silanol-terminated polydimethylsiloxane to give the title crownfunctionalized linear polysiloxane. It was found that the polysiloxane could be coordinated withplatinum salt to form platinum complex, which could catalyze the hydrosilylation of olefins withtriethoxysilane efficiently.
文摘Silica-bound 15-Crown-5, 18-Crown-6 with a spacer of propyloxymethyl and their platinum complexes have been synthesized. It was found that they were efficient catalysts for the hydrosilylation of olefms with triethoxysilane in the temperature range of 60 to 130 ℃.
文摘Fullerene n propylamine platinum,rhodium complex have been prepared from C 60 via amination with n propylamine, then reacting respectively with potassium chloroplatinite or rhodium chloride. The two noble metal complexes can effectively catalyze hydrosilylation of olefins with triethoxysilane. The Pt complex exhibits high regioselectivty for styrene, nearly 100% branched product is obtained.
文摘The synthesis of a new type of selena aza crown ether 6 (4 nitrobenzyl) 1,4,7,10 selenatriazacyclododecane (L) derivated from phenylalanine , and its platinum(Ⅱ) complex was described. The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.
文摘An electrode development was needed with high efficiency and low costs as next generation solar cells. We attempted the electrode fabrication for a photoelectrochemical cell by immobilizing functional groups on a n-Si(111) surface. The immobilization was applied by hydrosilylation terminated with ester (hydrophobic) or carbonyl (hydrophilic) group. Results confirmed the immobilization on the Si surface by measuring ATR-FTIR and XPS.
文摘The title complex (PtL_2Cl_2) was synthesized by reacting 10-selenabenzo-15-crown-5 (L) with potassium chloroplatinite. Its catalytic activity for the hydrosilylation of olefins by triethoxysilane, was investi gated.
文摘The syntheses of a new type of heteromacrocyclic polyether- 2,3-benzo-1,4,7,13-tetraoxa-10-telluracyclopentadeca-2-ene(L),and its pla- tinum complex(PtL_2Cl_2)were described.The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.
文摘Asymmetric hydrisilylation catalyzed by polymeric thiazolidine rhodium catalystswas conducted. Almost the same optical yields have been obtained when comb-shapedpolymeric ligands and their corresponding monomer complexed rhodium cataltystswere used to asymmetric hydrosilylation of acetophenone. Optical yield of chira 1- methylbenzyl alcohol reaches as high as 71.5%. Temperature dependence of enantio- selective hydrosilylation of acetophenone was discussed.
文摘With the increasing demand for homoallylic silanes and allylic silanes,the highly efficient and regioselective hydrosilylations of conjugated dienes are urgently needed.Herein,we developed a Ni-catalyzed regiodivergent hydrosilylation of aromatic conjugated dienes by adjusting the temperature and ligands.Under low temperature(-30℃),an eternal-ligand-free system(Ni/t-BuOk)can efficiently facilitate the 3,4-anti-Markovnikov hydrosilylation to provide homoallylic silanes via electrophilic activation process;under room temperature(25℃),a ligand-controlled system(Ni/t-BuOk/PPh3)can eventuate the 3,4-Markovnikov hydrosilylation to produce allylic silanes via Chalk-Harrod process.Both systems are compatible with various conjugated dienes and primary silanes in excellent yields andregioselectivities.
