The reduction of disulfides by samarium diiodide led to sa arium thiolates (ArSSml2).This new thiolate anion species reacted smoothly with α, β -unsaturated esters (nitriles) to give 1,4-addition products β -thioes...The reduction of disulfides by samarium diiodide led to sa arium thiolates (ArSSml2).This new thiolate anion species reacted smoothly with α, β -unsaturated esters (nitriles) to give 1,4-addition products β -thioesters and β -thionitriles in good yields under mild and neutralcondition.展开更多
Nitrodisulfides were reduced by SmI2/HMPA in anhydrous THF at room temperature to produce active intermediates (samarium thiolates and amides), which were 'living' double-anions and reacted smoothly with aldeh...Nitrodisulfides were reduced by SmI2/HMPA in anhydrous THF at room temperature to produce active intermediates (samarium thiolates and amides), which were 'living' double-anions and reacted smoothly with aldehydes or ketones to afford benzothiazolines in good yields under mild and neutral conditions.展开更多
o-Nitrophenylazide was reduced by SmI2 in anhydrous THF at room temperature to produce active intermediate 2 (samarium amide), "living" double-anion in situ which reacted smoothly with α,β-unsaturated ket...o-Nitrophenylazide was reduced by SmI2 in anhydrous THF at room temperature to produce active intermediate 2 (samarium amide), "living" double-anion in situ which reacted smoothly with α,β-unsaturated ketones to afford 2,3-dihydro-1H-1,5-benzodiazepines in good yields under mild and neutral conditions.展开更多
The reduction of elemental selenium by samarium diiodide led to selective formation of selenolate anion species (Se-2(2-) and Se2-), these nucleophilic species reacted readily with sodium alkyl thiosulfates to afford ...The reduction of elemental selenium by samarium diiodide led to selective formation of selenolate anion species (Se-2(2-) and Se2-), these nucleophilic species reacted readily with sodium alkyl thiosulfates to afford dithiodiselenides and dithioselenides in moderate to good yield under mild conditions.展开更多
1-(β-Hydroxyalkyl)-l,3,4-oxadiazole derivatives were synthesized via reductive addition reactions of 2-chloromethyl-l,3,4-oxadiazole with carbonyl compounds under mild conditions promoted by SmI2.
The two-dimensional(2D)ferromagnetic materials and the related van der Waals homostructures have attracted considerable interest,while the 2D antiferromagnetic material has not yet been reported.Based on first-princip...The two-dimensional(2D)ferromagnetic materials and the related van der Waals homostructures have attracted considerable interest,while the 2D antiferromagnetic material has not yet been reported.Based on first-principles calculations,we investigate both electronic structures and magnetic orderings of bulk and monolayer of chromium diiodides(CrI2).We demonstrate a counter-intuitive fact that the ground state of the free-standing monolayer of CrI2 is antiferromagnetic though the bulk possesses macroscopic ferromagnetic ordering.The interlayer interaction remains antiferromagnetic up to few-layer scenarios.The unique feature of CrI2 makes it an ideal workbench to investigate the relation between magnetic couplings and interlayer van der Waals interactions,and may offer an opportunity to 2D antiferromagnetic spintronic devices.展开更多
The Se-St bond in arylselenotrimethylsilane was reduced by samarium diiodide to produce samarium arylselenolate, which reacted with a,β-unsaturated esters or α,β-unsaturated nitriles to give β-selenoesters and β-...The Se-St bond in arylselenotrimethylsilane was reduced by samarium diiodide to produce samarium arylselenolate, which reacted with a,β-unsaturated esters or α,β-unsaturated nitriles to give β-selenoesters and β-selenonitriles, respectively.展开更多
Dihydro-(2H)-1 .2.4-benzothiadizine-1. 1-dioixdes were prepared in good yields via reductive cyclization of o-nitrobenzenesulfonamidcs with aldchydes promoted by Sml2 under mild and neutral condition.
The reduction of diacyl diselenides by samarium diiodide led to the production ofsamarium acylselenolates, which reacted with a,β-unsaturated esters or nitriles to give β-selenoesters or selenonitriles under mild an...The reduction of diacyl diselenides by samarium diiodide led to the production ofsamarium acylselenolates, which reacted with a,β-unsaturated esters or nitriles to give β-selenoesters or selenonitriles under mild and neutral conditions.展开更多
The results of diagnostics of spectral, temporal and energy characteristics of the radiation of gas-discharge plasma in a mixture of mercury diiodide vapor with helium in the spectral range of 350 - 900 nm, and the pl...The results of diagnostics of spectral, temporal and energy characteristics of the radiation of gas-discharge plasma in a mixture of mercury diiodide vapor with helium in the spectral range of 350 - 900 nm, and the plasma parameters in the range of reduced electric field E/N = 1 - 100 Td are presented. The plasma is created in the barrier discharge device with a cylindrical aperture. The electrodes are placed 0.2 m in length at a distance of 0.015 m. The amplitude of the pump pulse, the duration and frequency were 20 - 30 kV, 150 ns and 1 - 20 kHz, respectively. Radiation in the visible region of the spectrum of mercury monoiodide exciplex molecule is revealed. Regu larities in the optical characteristics of the plasma, depending on the partial pressures of the components of the mixture, the electron energy distribution function, mean electron energy, specific losses of discharge power on the process of dissociative excitation of mercury monoiodide (state B2Σ+1/2) molecules as well as the rate constant of dissociative excitation of mercury monoiodide molecules in working mixture depending on the given reduced electric field are established.展开更多
Samarium diiodide (SmI2) was found to be an efficient catalyst for the condensation of o-phenylenediamine and ketones to afford the corresponding 2,3-dihydro-1H-benzo[b][1,4]-diazepines in moderate to excellent yiel...Samarium diiodide (SmI2) was found to be an efficient catalyst for the condensation of o-phenylenediamine and ketones to afford the corresponding 2,3-dihydro-1H-benzo[b][1,4]-diazepines in moderate to excellent yields under very mild and solvent-free conditions. The real active species here was suggested to be a Sin(Ⅲ) intermediate formed in situ and the mechanism of the present reaction was proposed.展开更多
Ytterbium metal reacts with iodine to generate ytterbium diiodide directly, which can react with diselenides to form ytterbium selenolates (RSeYbI2). These species reacted smoothly with allyl bromide to give allylsele...Ytterbium metal reacts with iodine to generate ytterbium diiodide directly, which can react with diselenides to form ytterbium selenolates (RSeYbI2). These species reacted smoothly with allyl bromide to give allylselenides in moderate to good yields under neutral conditions.展开更多
Stereoselective Michael addition and Michael-aldol tandem reaction of diorganyl diselenides and disulfides with conjugated alkynones mediated by samarium diiodide were studied. The reaction temperature was critical fo...Stereoselective Michael addition and Michael-aldol tandem reaction of diorganyl diselenides and disulfides with conjugated alkynones mediated by samarium diiodide were studied. The reaction temperature was critical for the stereoselectivity. -Organylselenoalkenones or -organylthioalkenones and ?-organylselenoallylic alcohols or ?-organylthioallylic alcohols were prepared in good yields.展开更多
The asymmetric reductive coupling reaction of various acrylates derived from D-isosorbide and D-isomannide with acetophenone mediated by samarium diiodide to give both enantiomers of the optically active γ-butyrolact...The asymmetric reductive coupling reaction of various acrylates derived from D-isosorbide and D-isomannide with acetophenone mediated by samarium diiodide to give both enantiomers of the optically active γ-butyrolactone was described. The best enantiomeric excess of the products was 60%.展开更多
We study the thermal and electronic transport properties as well as the thermoelectric(TE)performance of three two-dimensional(2 D)XI_(2)(X=Ge,Sn,Pb)bilayers using density functional theory and Boltzmann transport the...We study the thermal and electronic transport properties as well as the thermoelectric(TE)performance of three two-dimensional(2 D)XI_(2)(X=Ge,Sn,Pb)bilayers using density functional theory and Boltzmann transport theory.We compared the lattice thermal conductivity,electrical conductivity,Seebeck coefficient,and dimensionless figure of merit(ZT)for the XI_(2)monolayers and bilayers.Our results show that the lattice thermal conductivity at room temperature for the bilayers is as low as~1.1 W·m^(-1)·K^(-1)-1.7 W·m^(-1)·K^(-1),which is about 1.6 times as large as the monolayers for all the three materials.Electronic structure calculations show that all the XI_(2)bilayers are indirect-gap semiconductors with the band gap values between 1.84 eV and 1.96 eV at PBE level,which is similar as the corresponding monolayers.The calculated results of ZT show that the bilayer structures display much less direction-dependent TE efficiency and have much larger n-type ZT values compared with the monolayers.The dramatic difference between the monolayer and bilayer indicates that the inter-layer interaction plays an important role in the TE performance of XI_(2),which provides the tunability on their TE characteristics.展开更多
Phenylthiotrimethylsilane is reduced hy samarium diiodide to yield samarium phenylthiolate. This new thiolate anion species reacts with acyl chlorides mildly to give thiolesters in good yields.
The crystal and molecular structure of 3,4-trans-4, 5-trans-2-amino-3cyano-1, 3-diethyloxy carbonyl-4, 5-di (4-chlorophenyl ) cyclopentene has been determined by X-ray diffraction method. The crystal (C24H22O4N2Cl2, M...The crystal and molecular structure of 3,4-trans-4, 5-trans-2-amino-3cyano-1, 3-diethyloxy carbonyl-4, 5-di (4-chlorophenyl ) cyclopentene has been determined by X-ray diffraction method. The crystal (C24H22O4N2Cl2, Mr = 473. 35) ismonoclinic with space group P21/c, a= 6. 923(1), b= 33. 178(5), c= 10. 644 (3)β=99. 86(2)°, V=2408. 8(8) A3, Z= 4, Dc= 1. 305g/cm3,μ(MoKa) = 3. 01cm-1,F(000) =984, R=0. 052, Rw=0. 067 for 2147 observed reflections (I】3(I)). Thephenyl groups and the alkoxy carbonyl group are in equatorial positions. The phenylgroups form dihedral angles bf 70. 67 and 66. 74° with the central five-membered ring.展开更多
The crystal and molecular structure of 4, 5-trans-2-amino-1, 3, 3-tri-cyano-4, 5-di(4-chlorophenyl) cyclopentene. ethanol - monohydrate has been deter-mined by X-ray diffraction method. The crystal (C20H12N4Cl2. C2H6O...The crystal and molecular structure of 4, 5-trans-2-amino-1, 3, 3-tri-cyano-4, 5-di(4-chlorophenyl) cyclopentene. ethanol - monohydrate has been deter-mined by X-ray diffraction method. The crystal (C20H12N4Cl2. C2H6O. H2O, Mr=443. 33) is triclinic with space group P1, a= 11. 033(4), b= 12. 199(3), c= 10. 732(3) A, a=114. 46(2), β=118. 33(3) γ=81. 56(3), V=1155- 1(7) A3, Z=2, Dc= 1. 275g/cm3, μ(MoKa) = 3. 05cm-1, F(000) = 460, R= 0. 070, Rw = 0. 089 for1965 observed reflections (I>3(I)). The phenyl groups are in equatorial positionsand form dihedral angles of 67. 89 and 63. 77° with the central 5-ring. X-ray analysisreveals that in the five membered ring the C (1) -C (2) bond is longer than normal double C=C bond while the C(2) -N (2) bond is shorter than normal C(sp)2-N bond.展开更多
文摘The reduction of disulfides by samarium diiodide led to sa arium thiolates (ArSSml2).This new thiolate anion species reacted smoothly with α, β -unsaturated esters (nitriles) to give 1,4-addition products β -thioesters and β -thionitriles in good yields under mild and neutralcondition.
基金We thank the National Natural Science Foundation of China (Project! No.29872010)the Laboratory of Organometallic Chemistry,
文摘Nitrodisulfides were reduced by SmI2/HMPA in anhydrous THF at room temperature to produce active intermediates (samarium thiolates and amides), which were 'living' double-anions and reacted smoothly with aldehydes or ketones to afford benzothiazolines in good yields under mild and neutral conditions.
基金We thank the National Natural Science Foundation of China (Project No.29872010) NSF of Zhejiang province for financial support.
文摘o-Nitrophenylazide was reduced by SmI2 in anhydrous THF at room temperature to produce active intermediate 2 (samarium amide), "living" double-anion in situ which reacted smoothly with α,β-unsaturated ketones to afford 2,3-dihydro-1H-1,5-benzodiazepines in good yields under mild and neutral conditions.
基金We are grateful to the National Natural Science Foundation of China(Project No.29872010)NSF of Zhejiang Province,China for the financial support.
文摘The reduction of elemental selenium by samarium diiodide led to selective formation of selenolate anion species (Se-2(2-) and Se2-), these nucleophilic species reacted readily with sodium alkyl thiosulfates to afford dithiodiselenides and dithioselenides in moderate to good yield under mild conditions.
基金the National Natural Science Foundation of China(Project No.20072033)the NSF of Zhejiang Province for financial support.
文摘1-(β-Hydroxyalkyl)-l,3,4-oxadiazole derivatives were synthesized via reductive addition reactions of 2-chloromethyl-l,3,4-oxadiazole with carbonyl compounds under mild conditions promoted by SmI2.
基金This work was supported by the National Natural Science Foundation of China(No.11404043)Graduate Research Innovation Project of Chongqing(No.CYS18253).
文摘The two-dimensional(2D)ferromagnetic materials and the related van der Waals homostructures have attracted considerable interest,while the 2D antiferromagnetic material has not yet been reported.Based on first-principles calculations,we investigate both electronic structures and magnetic orderings of bulk and monolayer of chromium diiodides(CrI2).We demonstrate a counter-intuitive fact that the ground state of the free-standing monolayer of CrI2 is antiferromagnetic though the bulk possesses macroscopic ferromagnetic ordering.The interlayer interaction remains antiferromagnetic up to few-layer scenarios.The unique feature of CrI2 makes it an ideal workbench to investigate the relation between magnetic couplings and interlayer van der Waals interactions,and may offer an opportunity to 2D antiferromagnetic spintronic devices.
文摘The Se-St bond in arylselenotrimethylsilane was reduced by samarium diiodide to produce samarium arylselenolate, which reacted with a,β-unsaturated esters or α,β-unsaturated nitriles to give β-selenoesters and β-selenonitriles, respectively.
文摘Dihydro-(2H)-1 .2.4-benzothiadizine-1. 1-dioixdes were prepared in good yields via reductive cyclization of o-nitrobenzenesulfonamidcs with aldchydes promoted by Sml2 under mild and neutral condition.
文摘The reduction of diacyl diselenides by samarium diiodide led to the production ofsamarium acylselenolates, which reacted with a,β-unsaturated esters or nitriles to give β-selenoesters or selenonitriles under mild and neutral conditions.
文摘The results of diagnostics of spectral, temporal and energy characteristics of the radiation of gas-discharge plasma in a mixture of mercury diiodide vapor with helium in the spectral range of 350 - 900 nm, and the plasma parameters in the range of reduced electric field E/N = 1 - 100 Td are presented. The plasma is created in the barrier discharge device with a cylindrical aperture. The electrodes are placed 0.2 m in length at a distance of 0.015 m. The amplitude of the pump pulse, the duration and frequency were 20 - 30 kV, 150 ns and 1 - 20 kHz, respectively. Radiation in the visible region of the spectrum of mercury monoiodide exciplex molecule is revealed. Regu larities in the optical characteristics of the plasma, depending on the partial pressures of the components of the mixture, the electron energy distribution function, mean electron energy, specific losses of discharge power on the process of dissociative excitation of mercury monoiodide (state B2Σ+1/2) molecules as well as the rate constant of dissociative excitation of mercury monoiodide molecules in working mixture depending on the given reduced electric field are established.
基金Project supported by the National Natural Science Foundation of China (No. 20272040), the State Key Laboratory of 0rganometallic Chemistry, Shanghai Institute of 0rganic Chemistry, Chinese Academy of Sciences and the Key Laboratory of 0rganic Synthesis of Jiangsu Province.
文摘Samarium diiodide (SmI2) was found to be an efficient catalyst for the condensation of o-phenylenediamine and ketones to afford the corresponding 2,3-dihydro-1H-benzo[b][1,4]-diazepines in moderate to excellent yields under very mild and solvent-free conditions. The real active species here was suggested to be a Sin(Ⅲ) intermediate formed in situ and the mechanism of the present reaction was proposed.
基金theEngineeringScienceResearchCenterofZhejiangUniversityofTechnology China
文摘Ytterbium metal reacts with iodine to generate ytterbium diiodide directly, which can react with diselenides to form ytterbium selenolates (RSeYbI2). These species reacted smoothly with allyl bromide to give allylselenides in moderate to good yields under neutral conditions.
基金the National Natural Science Foundation of China (No. 20072033) and the Specialized Research Fund for the Doctoral Program of Higher Education of China.
文摘Stereoselective Michael addition and Michael-aldol tandem reaction of diorganyl diselenides and disulfides with conjugated alkynones mediated by samarium diiodide were studied. The reaction temperature was critical for the stereoselectivity. -Organylselenoalkenones or -organylthioalkenones and ?-organylselenoallylic alcohols or ?-organylthioallylic alcohols were prepared in good yields.
基金Project (No. 297912045) supported by the National Natural Science Foundation of China
文摘The asymmetric reductive coupling reaction of various acrylates derived from D-isosorbide and D-isomannide with acetophenone mediated by samarium diiodide to give both enantiomers of the optically active γ-butyrolactone was described. The best enantiomeric excess of the products was 60%.
基金Project supported by the Fundamental Research Fund for the Central Universities and the Zhongying Young Scholar Program of Southeast University。
文摘We study the thermal and electronic transport properties as well as the thermoelectric(TE)performance of three two-dimensional(2 D)XI_(2)(X=Ge,Sn,Pb)bilayers using density functional theory and Boltzmann transport theory.We compared the lattice thermal conductivity,electrical conductivity,Seebeck coefficient,and dimensionless figure of merit(ZT)for the XI_(2)monolayers and bilayers.Our results show that the lattice thermal conductivity at room temperature for the bilayers is as low as~1.1 W·m^(-1)·K^(-1)-1.7 W·m^(-1)·K^(-1),which is about 1.6 times as large as the monolayers for all the three materials.Electronic structure calculations show that all the XI_(2)bilayers are indirect-gap semiconductors with the band gap values between 1.84 eV and 1.96 eV at PBE level,which is similar as the corresponding monolayers.The calculated results of ZT show that the bilayer structures display much less direction-dependent TE efficiency and have much larger n-type ZT values compared with the monolayers.The dramatic difference between the monolayer and bilayer indicates that the inter-layer interaction plays an important role in the TE performance of XI_(2),which provides the tunability on their TE characteristics.
文摘Phenylthiotrimethylsilane is reduced hy samarium diiodide to yield samarium phenylthiolate. This new thiolate anion species reacts with acyl chlorides mildly to give thiolesters in good yields.
文摘The crystal and molecular structure of 3,4-trans-4, 5-trans-2-amino-3cyano-1, 3-diethyloxy carbonyl-4, 5-di (4-chlorophenyl ) cyclopentene has been determined by X-ray diffraction method. The crystal (C24H22O4N2Cl2, Mr = 473. 35) ismonoclinic with space group P21/c, a= 6. 923(1), b= 33. 178(5), c= 10. 644 (3)β=99. 86(2)°, V=2408. 8(8) A3, Z= 4, Dc= 1. 305g/cm3,μ(MoKa) = 3. 01cm-1,F(000) =984, R=0. 052, Rw=0. 067 for 2147 observed reflections (I】3(I)). Thephenyl groups and the alkoxy carbonyl group are in equatorial positions. The phenylgroups form dihedral angles bf 70. 67 and 66. 74° with the central five-membered ring.
文摘The crystal and molecular structure of 4, 5-trans-2-amino-1, 3, 3-tri-cyano-4, 5-di(4-chlorophenyl) cyclopentene. ethanol - monohydrate has been deter-mined by X-ray diffraction method. The crystal (C20H12N4Cl2. C2H6O. H2O, Mr=443. 33) is triclinic with space group P1, a= 11. 033(4), b= 12. 199(3), c= 10. 732(3) A, a=114. 46(2), β=118. 33(3) γ=81. 56(3), V=1155- 1(7) A3, Z=2, Dc= 1. 275g/cm3, μ(MoKa) = 3. 05cm-1, F(000) = 460, R= 0. 070, Rw = 0. 089 for1965 observed reflections (I>3(I)). The phenyl groups are in equatorial positionsand form dihedral angles of 67. 89 and 63. 77° with the central 5-ring. X-ray analysisreveals that in the five membered ring the C (1) -C (2) bond is longer than normal double C=C bond while the C(2) -N (2) bond is shorter than normal C(sp)2-N bond.