Conversion of alkynes to alkenes by photocatalysis has inspired extensive interest but it is still challenging to obtain both high conversion and selectivity.Here we first demonstrate the photocatalytic conversion of ...Conversion of alkynes to alkenes by photocatalysis has inspired extensive interest but it is still challenging to obtain both high conversion and selectivity.Here we first demonstrate the photocatalytic conversion of phenylacetylene(PLE)to styrene(STE)with both high conversion and selectivity by using the titania(TiO2)supported platinum(Pt)as photocatalyst under 385 nm monochromatic light irradiation.It is demonstrated that the conversion rate of PLE is strongly dependent on the content of Pt cocatalyst loaded on the surface of TiO2.Based on our optimization,the conversion of PLE and the selectivity towards STE on the 1 wt%Pt/TiO2 photocatalyst can unexpectedly reach as high as 92.4%and 91.3%,respectively.The highly selective photocatalytic hydrogenation can well be extended to the conversion of other typical alkynes to alkenes,demonstrating the generality of selective hydrogenation of C≡C over the Pt/TiO2 photocatalyst.展开更多
The adsorption configurations of molecules adsorbed on substrates can significantly affect their physical and chemical properties. A standing configuration can be difficult to determine by traditional techniques, such...The adsorption configurations of molecules adsorbed on substrates can significantly affect their physical and chemical properties. A standing configuration can be difficult to determine by traditional techniques, such as scanning tunneling microscopy(STM) due to the superposition of electronic states. In this paper, we report the real-space observation of the standing adsorption configuration of phenylacetylene on Cu(111) by non-contact atomic force microscopy(nc-AFM).Deposition of phenylacetylene at 25 K shows featureless bright spots in STM images. Using nc-AFM, the line features representing the C–H and C–C bonds in benzene rings are evident, which implies a standing adsorption configuration. Further density functional theory(DFT) calculations reveal multiple optimized adsorption configurations with phenylacetylene breaking its acetylenic bond and forming C–Cu bond(s) with the underlying copper atoms, and hence stand on the substrate.By comparing the nc-AFM simulations with the experimental observation, we identify the standing adsorption configuration of phenylacetylene on Cu(111). Our work demonstrates an application of combining nc-AFM measurements and DFT calculations to the study of standing molecules on substrates, which enriches our knowledge of the adsorption behaviors of small molecules on solid surfaces at low temperatures.展开更多
The hydration of phenylacetylene in near-critical water,assisted with additives（NaHSO4,ZnCl2,FeCl3）,has been successfully conducted with temperature and residence time ranges of 220-300℃and 60-180 min,respectively....The hydration of phenylacetylene in near-critical water,assisted with additives（NaHSO4,ZnCl2,FeCl3）,has been successfully conducted with temperature and residence time ranges of 220-300℃and 60-180 min,respectively.The results showed the catalytic ability is FeCl3ZnCl2NaHSO4.The maximum yield of product acetophenone was 96.68%at 260℃,120 min.Based on the results found,a possible mechanism of hydration of phenylacetylene in near-critical water was proposed.展开更多
Electronic transport properties of a kind of phenylacetylene compound-- （4-mercaptophenyl）-phenylacetylene are calculated by the first-principles method in the framework of density functional theory and the nonequil...Electronic transport properties of a kind of phenylacetylene compound-- （4-mercaptophenyl）-phenylacetylene are calculated by the first-principles method in the framework of density functional theory and the nonequilibrium Green＇s function formalism. The molecular junction shows an obvious rectifying behaviour at a bias voltage larger than 1.0 V. The rectification effect is attributed to the asymmetry of the interface contacts. Moreover, at a bias voltage larger than 2.0 V, which is not referred to in a relevant experiment [Fang L, Park J Y, Ma H, Jen A K Y and Salmeron M 2007 Langmuir 23 11522], we find a negative differential resistance phenomenon. The negative differential resistance effect may originate from the change of the delocalization degree of the molecular orbitals induced by the bias.展开更多
The isomerization of pendant groups plays a crucial role in modulating helical structures and biological activity in both biomacromolecule and dynamic helical conjugated polymers.While the effects of solvents,pH,and t...The isomerization of pendant groups plays a crucial role in modulating helical structures and biological activity in both biomacromolecule and dynamic helical conjugated polymers.While the effects of solvents,pH,and temperature on pendant isomerization and helix preference have been extensively studied,the combined influence of pendant isomerization and enantiomeric excess remains largely unexplored.Herein,we report a dynamic helical poly(phenylacetylene)(PPA)system,poly-[D_(r)-co-L_(1-r)],in which the helix preference is dictated and nonlinearly amplified via the“majority rule”mechanism at low temperatures.Remarkably,temperature-triggered pendant isomerization can override this helix preference,leading to an“abnormal majority rule”behavior.By harnessing these dual effects,precise helix regulation is achieved,enabling helix inversion at high enantiomeric excess and chiral sustenance at low enantiomeric excess.A bifurcation point in helix preference facilitates the orthogonal control of polymer helicity,paving the way for programmable circularly polarized luminescence microarrays,with potential applications in information encoding and anticounterfeiting technologies.These findings provide a strategy for fine-tuning dynamic helical polymer structures.展开更多
The Pt-Ni nanoframe catalysts have attracted great interest owing to their unique electronic structure and excellent catalytic performance. However, the stability of the tenu ous edges of nano frame-structures is diss...The Pt-Ni nanoframe catalysts have attracted great interest owing to their unique electronic structure and excellent catalytic performance. However, the stability of the tenu ous edges of nano frame-structures is dissatisfactory and their un iversal applicati ons in catalytic market beyond electrocatalytic reactions are yet to be tapped and explored. Herein, we developed a new core@ shell structured Pt-Ni nanoframe@CeO2 (Pt-Ni NF@CeO2) composite via etching the Ni from inhomogeneous Pt-Ni rhombic dodecahedra (Pt-Ni RD) by cerium(lll) acetate hydrate (Ce(OAc)3). In this path, Pt-Ni RD was used as self-sacrificial 怕mplate, while the Ce(OAc)3 serves as the provider of the Ce3* source and OH' for the formation of CeO2 shell, etchant of Pt-Ni RD, and the surface modification agent. By this way, the etching of Pt-Ni RD and the formation of the CeO2 shell are simultaneously proceeded to form the final Pt-Ni NF@CeO2 in one step. The obtained Pt-Ni NF@CeO2 exhibits strong in terfacial charge tran sfer interactio n betwee n Pt-Ni NF core and CeO2 shell eve n without reductio n treatment, leading to enhan ced catalytic activity in the hydrogenation of phenylacetylene. After introduction of trace silver, the Pt-Ni-Ag4.9 NF@CeO2 achieves remarkable catalytic performa nee for the selective con versi on of phe ny lacetyle ne to styrene: high con version (100%), styre ne selectivity (86.5%), and good stability. It reveals that enc apsulatio n n oble metal nano frames into metal oxide to form core @ shell structured hybrids will in deed enhance their stability and catalytic properties. Particularly, this work expends the application of noble metal nanoframes materials to hydrogenation reacti ons.展开更多
Selective semi-hydrogenation of phenylacetylene to styrene is a crucial step in the polystyrene industry.Although Pd-based catalysts are widely used in this reaction due to their excellent hydrogenation activity,the s...Selective semi-hydrogenation of phenylacetylene to styrene is a crucial step in the polystyrene industry.Although Pd-based catalysts are widely used in this reaction due to their excellent hydrogenation activity,the selectivity for styrene remains a great challenge.Herein,we designed a mesoporous silica stabilized Pd-Ru@ZIF-8(MS Pd-Ru@ZIF-8)nanoreactor with novel Pd and Ru single site synergistic catalytical system for semi-hydrogenation of phenylacetylene.The nanoreactor exhibited a superior performance,achieving 98%conversion of phenylacetylene and 96%selectivity to styrene.Turnover frequency(TOF)of nanoreactor was up to as high as 2,188 h^(−1),which was 25 times and 5 times more than the single metal species catalysts,mesoporous silica stabilized Pd@ZIF-8 nanoreactor(MS Pd@ZIF-8),and mesoporous silica stabilized Ru@ZIF-8 nanoreactor(MS Ru@ZIF-8).This catalytic activity was attributed to the synergistic effect of Pd and Ru single site anchored strongly into the framework of ZIF-8,which reduced the desorption energy of styrene and increased the hydrogenation energy barrier of styrene.Importantly,since the ordered mesoporous silica was introduced into the nanoreactor shell to stabilize ZIF-8,MS Pd-Ru@ZIF-8 showed excellent reusability and stability.After the five cycles,the catalytical activity and selectivity still remained.This work provides insights for a synergistic catalytic system based on single-site active sites for selective hydrogenation reactions.展开更多
Two ligand bridged binuclear titanium complexes Ti2（bppda）3（NMe2）2·3THF （1） and Ti2（bppda）3（NEt2）2·3THF （2） and one bis-ligand coordinated mononuclear complex Ti（bppda）2 （3） （ligand- HEbppda...Two ligand bridged binuclear titanium complexes Ti2（bppda）3（NMe2）2·3THF （1） and Ti2（bppda）3（NEt2）2·3THF （2） and one bis-ligand coordinated mononuclear complex Ti（bppda）2 （3） （ligand- HEbppda=N,N＇-Bis（2-pyrrylmeth- ylidene）-1,2-phenylenediamine） were synthesized by adjusting the ratio of the starting materials and the reaction speed. The complexes were fully characterized with NMR, elemental analysis and X-ray crystal diffraction. The catalytic activity of the complex 1 to phenylacetylene hydroanilination reaction was also investigated.展开更多
UV irradiation of N-methyl-2,3-naphthalenedicarboximide with phenylacetylene in benzene solution afforded a novel hexacyclic adduct 2 confirmed unambiguously by single crystal X-ray diffraction.
（S）-（1-Benzylpyrrolidin-2-yl）diphenylmethanol and cinchonine were evaluated as promotors in the asymmetric additions of phenylacetylene to ketones, in order to prepare chiral propargylic alcohols. Good yields （up...（S）-（1-Benzylpyrrolidin-2-yl）diphenylmethanol and cinchonine were evaluated as promotors in the asymmetric additions of phenylacetylene to ketones, in order to prepare chiral propargylic alcohols. Good yields （up to 89%） and moderate enantioselectivities （up to 77.9% ee） were achieved. Addition of Ti（OPr-i）4 can significantly improve the enantioselectivity of the reaction.展开更多
Catalytic selective hydrogenation of alkynes to the corresponding alkenes is an important process in industrial production.Modulating the selective hydrogenation of alkynes to the alkenes requires ingenuity since alke...Catalytic selective hydrogenation of alkynes to the corresponding alkenes is an important process in industrial production.Modulating the selective hydrogenation of alkynes to the alkenes requires ingenuity since alkenes can easily be converted into the corresponding alkanes under reductive conditions.Applying different reductive reagents to prevent the direct usage of H_(2)can avoid difficulties in hydrogen storage and transportation.Herein,we demonstrate a tandem process to hydrogenate phenylacetylene by CO and H_(2)Oviathecouplingof thelow-temperaturewater-gas shift reaction and selective hydrogenation of phenylacetylene utilizing theα-MoC catalyst.The reductive reagent,CO,not only produces H_(2)from H_(2)O to drive the reaction forward,but it also regulates the selectivity of styrene by preventing further hydrogenation.展开更多
The copolymerization of p-diethynylbenzene (PDEB) with phenylacetylene (PhA), 4, 4'-diethynylbiphenyl (DEBP)or m-diethynylbenzene (MDEB) are studied by varying mole ratios of monomers. When the mole ratios of PDEB...The copolymerization of p-diethynylbenzene (PDEB) with phenylacetylene (PhA), 4, 4'-diethynylbiphenyl (DEBP)or m-diethynylbenzene (MDEB) are studied by varying mole ratios of monomers. When the mole ratios of PDEB/PhA are less or equal to 1/5, the copolymers are soluble and fusible, but the other copolymers are insoluble and infusible. The results show that the good solvent of cross-linked copolymers is benzene and their solubility parameter is 9.15 cal^(0.5).cm(-1.5). And their swellability (θ_p), Huggins parameter (χ), density (d_4^(25)) and the average molecular weights between crosslinks (c) are measured. It is found that θp and c of copolymers are greater but d_4^(25) is less than that of respective homopolymers. IR spectra show that the copolymers have transoid configuration and small number of unreacted ethynyl groups exist in the copolymers. The mechanism about the polymerization or acetylenic derivatives initiated by (Ph_3P)_2PdCl_2 is discussed.展开更多
Two acetylene polymers containing cyanobiphenyl-based mesogens, poly{10-[((4'-cyano-4-biphenylyl)oxy)carbonyl]-1-decyne} (PA8CN), which has a relatively flexible polyalkyne backbone, and poly {[4-(((12-((4'-cy...Two acetylene polymers containing cyanobiphenyl-based mesogens, poly{10-[((4'-cyano-4-biphenylyl)oxy)carbonyl]-1-decyne} (PA8CN), which has a relatively flexible polyalkyne backbone, and poly {[4-(((12-((4'-cyano-4-biphenylyl)oxy)dodecyl)oxy) carbonyl) phenyl]-acetylene} (PB12CN), which has a fairly rigid poly(phenylacetylene) backbone, were synthesized using respectively WCl6 and [Rh(nbd)Cl](2) as the catalysts. PA8CN exhibits enantiotropic interdigitated smectic A phase (S-Ad) over a temperature range as wide as ca. 100 degrees C, whereas PB12CN is non-mesomorphic, demonstrating that the backbone rigidity plays an important role in determining the liquid crystallinity of the polyacetylenes.展开更多
he reaction of (2, 4-C_7H_11)_3Nd with HC=CC_6H_5 in toluene leads to [(2, 4-C_7H_11)_2NdC = CC_6H_5]_2 , which crystallizes in the space group P_cab with unit cell pa-rameters a=1 . 0489 (11), b=1.8033 (12), c=2. 106...he reaction of (2, 4-C_7H_11)_3Nd with HC=CC_6H_5 in toluene leads to [(2, 4-C_7H_11)_2NdC = CC_6H_5]_2 , which crystallizes in the space group P_cab with unit cell pa-rameters a=1 . 0489 (11), b=1.8033 (12), c=2. 1064 (15)nm and Z=4 , least-squares refinement based on 2323 observed reflections converged to a final R valueof 0. 08. The molecular structure shows that the complex is a dimer, in which two(2,4-C_7H_11)_2Nd units are connected by asymmetrical alkynide bridges with indepen-dent Nd-C(alkynide) bond lengths of 0. 2552(25)and 0. 2560(24)nm, Nd-C=C angles of 124. 1(17)° and 134. 2(17)°.展开更多
基金supported by the National Natural Science Foundation of China(21633009)Dalian Science Foundation for Distinguished Young Scholars(2017RJ02)the Liaoning Revitalization Talents Program(XLYC1807241)~~
文摘Conversion of alkynes to alkenes by photocatalysis has inspired extensive interest but it is still challenging to obtain both high conversion and selectivity.Here we first demonstrate the photocatalytic conversion of phenylacetylene(PLE)to styrene(STE)with both high conversion and selectivity by using the titania(TiO2)supported platinum(Pt)as photocatalyst under 385 nm monochromatic light irradiation.It is demonstrated that the conversion rate of PLE is strongly dependent on the content of Pt cocatalyst loaded on the surface of TiO2.Based on our optimization,the conversion of PLE and the selectivity towards STE on the 1 wt%Pt/TiO2 photocatalyst can unexpectedly reach as high as 92.4%and 91.3%,respectively.The highly selective photocatalytic hydrogenation can well be extended to the conversion of other typical alkynes to alkenes,demonstrating the generality of selective hydrogenation of C≡C over the Pt/TiO2 photocatalyst.
基金Project supported by the National Key Research and Development Program of China(Grant Nos.2016YFA0202300 and 2018YFA0305800)the National Natural Science Foundation of China(Grant Nos.61888102,61474141,and 21661132006)+2 种基金the Young Scientists Fund of the National Natural Science Foundation of China(Grant No.11604373)the Outstanding Youth Science Foundation,China(Grant No.61622116)the Strategic Priority Research Program of Chinese Academy of Sciences(CAS)(Grant Nos.XDB28000000 and XDB30000000)
文摘The adsorption configurations of molecules adsorbed on substrates can significantly affect their physical and chemical properties. A standing configuration can be difficult to determine by traditional techniques, such as scanning tunneling microscopy(STM) due to the superposition of electronic states. In this paper, we report the real-space observation of the standing adsorption configuration of phenylacetylene on Cu(111) by non-contact atomic force microscopy(nc-AFM).Deposition of phenylacetylene at 25 K shows featureless bright spots in STM images. Using nc-AFM, the line features representing the C–H and C–C bonds in benzene rings are evident, which implies a standing adsorption configuration. Further density functional theory(DFT) calculations reveal multiple optimized adsorption configurations with phenylacetylene breaking its acetylenic bond and forming C–Cu bond(s) with the underlying copper atoms, and hence stand on the substrate.By comparing the nc-AFM simulations with the experimental observation, we identify the standing adsorption configuration of phenylacetylene on Cu(111). Our work demonstrates an application of combining nc-AFM measurements and DFT calculations to the study of standing molecules on substrates, which enriches our knowledge of the adsorption behaviors of small molecules on solid surfaces at low temperatures.
基金supported by the National Natural Science Foundation of China(Nos.21073064,21003049)
文摘The hydration of phenylacetylene in near-critical water,assisted with additives（NaHSO4,ZnCl2,FeCl3）,has been successfully conducted with temperature and residence time ranges of 220-300℃and 60-180 min,respectively.The results showed the catalytic ability is FeCl3ZnCl2NaHSO4.The maximum yield of product acetophenone was 96.68%at 260℃,120 min.Based on the results found,a possible mechanism of hydration of phenylacetylene in near-critical water was proposed.
基金Supported by NSFC (20372028) the Ministry of Science and Technology of China the Teaching and Research Award Program for Outstanding Young Teachers of MOE of China.
基金supported by the Special Funds of the National Natural Science Foundation of China (Grant No. 11047148)the Jining University Research Program, China (Grant No. 2010QNKJ04)
文摘Electronic transport properties of a kind of phenylacetylene compound-- （4-mercaptophenyl）-phenylacetylene are calculated by the first-principles method in the framework of density functional theory and the nonequilibrium Green＇s function formalism. The molecular junction shows an obvious rectifying behaviour at a bias voltage larger than 1.0 V. The rectification effect is attributed to the asymmetry of the interface contacts. Moreover, at a bias voltage larger than 2.0 V, which is not referred to in a relevant experiment [Fang L, Park J Y, Ma H, Jen A K Y and Salmeron M 2007 Langmuir 23 11522], we find a negative differential resistance phenomenon. The negative differential resistance effect may originate from the change of the delocalization degree of the molecular orbitals induced by the bias.
基金supported by the National Natural Science Foundation of China(52373122)Fundamental Research Funds for the Central Universities(WK2060000071)+2 种基金Youth Project of the Provincial Natural Science Foundation of Anhui(2408085QB041)the open research fund of Suzhou Laboratory(SZLAB-1508-2024-ZD017)AnHui Estone Materials Technology Co.,Ltd.This work was partially carried out at the University of Science and Technology of China’s Center for Micro and Nanoscale Research and Fabrication and Instruments Center for Physical Science.
文摘The isomerization of pendant groups plays a crucial role in modulating helical structures and biological activity in both biomacromolecule and dynamic helical conjugated polymers.While the effects of solvents,pH,and temperature on pendant isomerization and helix preference have been extensively studied,the combined influence of pendant isomerization and enantiomeric excess remains largely unexplored.Herein,we report a dynamic helical poly(phenylacetylene)(PPA)system,poly-[D_(r)-co-L_(1-r)],in which the helix preference is dictated and nonlinearly amplified via the“majority rule”mechanism at low temperatures.Remarkably,temperature-triggered pendant isomerization can override this helix preference,leading to an“abnormal majority rule”behavior.By harnessing these dual effects,precise helix regulation is achieved,enabling helix inversion at high enantiomeric excess and chiral sustenance at low enantiomeric excess.A bifurcation point in helix preference facilitates the orthogonal control of polymer helicity,paving the way for programmable circularly polarized luminescence microarrays,with potential applications in information encoding and anticounterfeiting technologies.These findings provide a strategy for fine-tuning dynamic helical polymer structures.
基金National Natural Science Foundation of China (Nos. 21590794, 21771173, and 21521092)project development plan of science and technology of Jilin Province (Nos. 20180101179JC and 20160520126JH)CAS-CSIRO project (GJHZ1730).
文摘The Pt-Ni nanoframe catalysts have attracted great interest owing to their unique electronic structure and excellent catalytic performance. However, the stability of the tenu ous edges of nano frame-structures is dissatisfactory and their un iversal applicati ons in catalytic market beyond electrocatalytic reactions are yet to be tapped and explored. Herein, we developed a new core@ shell structured Pt-Ni nanoframe@CeO2 (Pt-Ni NF@CeO2) composite via etching the Ni from inhomogeneous Pt-Ni rhombic dodecahedra (Pt-Ni RD) by cerium(lll) acetate hydrate (Ce(OAc)3). In this path, Pt-Ni RD was used as self-sacrificial 怕mplate, while the Ce(OAc)3 serves as the provider of the Ce3* source and OH' for the formation of CeO2 shell, etchant of Pt-Ni RD, and the surface modification agent. By this way, the etching of Pt-Ni RD and the formation of the CeO2 shell are simultaneously proceeded to form the final Pt-Ni NF@CeO2 in one step. The obtained Pt-Ni NF@CeO2 exhibits strong in terfacial charge tran sfer interactio n betwee n Pt-Ni NF core and CeO2 shell eve n without reductio n treatment, leading to enhan ced catalytic activity in the hydrogenation of phenylacetylene. After introduction of trace silver, the Pt-Ni-Ag4.9 NF@CeO2 achieves remarkable catalytic performa nee for the selective con versi on of phe ny lacetyle ne to styrene: high con version (100%), styre ne selectivity (86.5%), and good stability. It reveals that enc apsulatio n n oble metal nano frames into metal oxide to form core @ shell structured hybrids will in deed enhance their stability and catalytic properties. Particularly, this work expends the application of noble metal nanoframes materials to hydrogenation reacti ons.
基金the financial support from the Beijing Natural Science Foundation(No.2182061)Science Foundation of China University of Petroleum,Beijing(No.2462019BJRC001)。
文摘Selective semi-hydrogenation of phenylacetylene to styrene is a crucial step in the polystyrene industry.Although Pd-based catalysts are widely used in this reaction due to their excellent hydrogenation activity,the selectivity for styrene remains a great challenge.Herein,we designed a mesoporous silica stabilized Pd-Ru@ZIF-8(MS Pd-Ru@ZIF-8)nanoreactor with novel Pd and Ru single site synergistic catalytical system for semi-hydrogenation of phenylacetylene.The nanoreactor exhibited a superior performance,achieving 98%conversion of phenylacetylene and 96%selectivity to styrene.Turnover frequency(TOF)of nanoreactor was up to as high as 2,188 h^(−1),which was 25 times and 5 times more than the single metal species catalysts,mesoporous silica stabilized Pd@ZIF-8 nanoreactor(MS Pd@ZIF-8),and mesoporous silica stabilized Ru@ZIF-8 nanoreactor(MS Ru@ZIF-8).This catalytic activity was attributed to the synergistic effect of Pd and Ru single site anchored strongly into the framework of ZIF-8,which reduced the desorption energy of styrene and increased the hydrogenation energy barrier of styrene.Importantly,since the ordered mesoporous silica was introduced into the nanoreactor shell to stabilize ZIF-8,MS Pd-Ru@ZIF-8 showed excellent reusability and stability.After the five cycles,the catalytical activity and selectivity still remained.This work provides insights for a synergistic catalytic system based on single-site active sites for selective hydrogenation reactions.
基金Project supported by the Science Foundation of Jiangsu Province （No. BK2005030）Acknowledgements Li Yahong thanks Aaron 0dom of Michigan State University for many helpful discussions and the authors appreciate the aid of Zhang Wenhua with the X-ray diffraction studies.
文摘Two ligand bridged binuclear titanium complexes Ti2（bppda）3（NMe2）2·3THF （1） and Ti2（bppda）3（NEt2）2·3THF （2） and one bis-ligand coordinated mononuclear complex Ti（bppda）2 （3） （ligand- HEbppda=N,N＇-Bis（2-pyrrylmeth- ylidene）-1,2-phenylenediamine） were synthesized by adjusting the ratio of the starting materials and the reaction speed. The complexes were fully characterized with NMR, elemental analysis and X-ray crystal diffraction. The catalytic activity of the complex 1 to phenylacetylene hydroanilination reaction was also investigated.
文摘UV irradiation of N-methyl-2,3-naphthalenedicarboximide with phenylacetylene in benzene solution afforded a novel hexacyclic adduct 2 confirmed unambiguously by single crystal X-ray diffraction.
文摘（S）-（1-Benzylpyrrolidin-2-yl）diphenylmethanol and cinchonine were evaluated as promotors in the asymmetric additions of phenylacetylene to ketones, in order to prepare chiral propargylic alcohols. Good yields （up to 89%） and moderate enantioselectivities （up to 77.9% ee） were achieved. Addition of Ti（OPr-i）4 can significantly improve the enantioselectivity of the reaction.
基金the Natural Science Foundation of China(grant nos.21725301,21932002,and 21821004)the National Key R&D Program of China(grant no.2021YFA1501102)China Petrochemical Corporation(grant no.420043-10).
文摘Catalytic selective hydrogenation of alkynes to the corresponding alkenes is an important process in industrial production.Modulating the selective hydrogenation of alkynes to the alkenes requires ingenuity since alkenes can easily be converted into the corresponding alkanes under reductive conditions.Applying different reductive reagents to prevent the direct usage of H_(2)can avoid difficulties in hydrogen storage and transportation.Herein,we demonstrate a tandem process to hydrogenate phenylacetylene by CO and H_(2)Oviathecouplingof thelow-temperaturewater-gas shift reaction and selective hydrogenation of phenylacetylene utilizing theα-MoC catalyst.The reductive reagent,CO,not only produces H_(2)from H_(2)O to drive the reaction forward,but it also regulates the selectivity of styrene by preventing further hydrogenation.
文摘The copolymerization of p-diethynylbenzene (PDEB) with phenylacetylene (PhA), 4, 4'-diethynylbiphenyl (DEBP)or m-diethynylbenzene (MDEB) are studied by varying mole ratios of monomers. When the mole ratios of PDEB/PhA are less or equal to 1/5, the copolymers are soluble and fusible, but the other copolymers are insoluble and infusible. The results show that the good solvent of cross-linked copolymers is benzene and their solubility parameter is 9.15 cal^(0.5).cm(-1.5). And their swellability (θ_p), Huggins parameter (χ), density (d_4^(25)) and the average molecular weights between crosslinks (c) are measured. It is found that θp and c of copolymers are greater but d_4^(25) is less than that of respective homopolymers. IR spectra show that the copolymers have transoid configuration and small number of unreacted ethynyl groups exist in the copolymers. The mechanism about the polymerization or acetylenic derivatives initiated by (Ph_3P)_2PdCl_2 is discussed.
基金This work was in part supported by the Hong Kong RGC grants HKUST597/95P and HKUST6149/97P.
文摘Two acetylene polymers containing cyanobiphenyl-based mesogens, poly{10-[((4'-cyano-4-biphenylyl)oxy)carbonyl]-1-decyne} (PA8CN), which has a relatively flexible polyalkyne backbone, and poly {[4-(((12-((4'-cyano-4-biphenylyl)oxy)dodecyl)oxy) carbonyl) phenyl]-acetylene} (PB12CN), which has a fairly rigid poly(phenylacetylene) backbone, were synthesized using respectively WCl6 and [Rh(nbd)Cl](2) as the catalysts. PA8CN exhibits enantiotropic interdigitated smectic A phase (S-Ad) over a temperature range as wide as ca. 100 degrees C, whereas PB12CN is non-mesomorphic, demonstrating that the backbone rigidity plays an important role in determining the liquid crystallinity of the polyacetylenes.
文摘he reaction of (2, 4-C_7H_11)_3Nd with HC=CC_6H_5 in toluene leads to [(2, 4-C_7H_11)_2NdC = CC_6H_5]_2 , which crystallizes in the space group P_cab with unit cell pa-rameters a=1 . 0489 (11), b=1.8033 (12), c=2. 1064 (15)nm and Z=4 , least-squares refinement based on 2323 observed reflections converged to a final R valueof 0. 08. The molecular structure shows that the complex is a dimer, in which two(2,4-C_7H_11)_2Nd units are connected by asymmetrical alkynide bridges with indepen-dent Nd-C(alkynide) bond lengths of 0. 2552(25)and 0. 2560(24)nm, Nd-C=C angles of 124. 1(17)° and 134. 2(17)°.
