The neutral palladium（Ⅱ） complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-imidazolyl]dichloropalladium（Ⅱ）（1A） ligated by thiazolylimidazolyl-based phosphine（L1） in which thiazolylimidazolyl acted as an...The neutral palladium（Ⅱ） complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-imidazolyl]dichloropalladium（Ⅱ）（1A） ligated by thiazolylimidazolyl-based phosphine（L1） in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-3-methylimidazolium]dichloropalladium（Ⅱ） trifluoromethanesulfonate（2A） ligated by thiazolylimidazolium-based phosphine（L2） after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.展开更多
C50H46OP4ClRh, RhCl(dppm)2 · H2O, Mr = 922. 2, monoclinic, P21/2, a=10. 532(3), b=22.574(8), c=18. 641(8) A, β=93. 41(3)°, V = 4424 (3) A3, Z = 4, Dc=1. 386 g. cm-3, λ(MoKα) = 0. 71073A , F(000) = 1904. T...C50H46OP4ClRh, RhCl(dppm)2 · H2O, Mr = 922. 2, monoclinic, P21/2, a=10. 532(3), b=22.574(8), c=18. 641(8) A, β=93. 41(3)°, V = 4424 (3) A3, Z = 4, Dc=1. 386 g. cm-3, λ(MoKα) = 0. 71073A , F(000) = 1904. The structure was determined by direct methods and difference Fourier syntheses and refined by full-matrix least-squares to final R = 0. 037 and Rw = 0. 036 for 3432 (F> 6. 0σ(F) ) observed reflections. The structure of the title compound contains RhCl-(dppm)2 and non-coordinated H2O molecules. The rhodium atom is coordinated by one chlorine atom and four phosphorus atoms of two DPPM ligands forming a tetragonal pyramidal configuration.展开更多
The title compound 〔(PPh 3)(CH 3COS) 2NiB 10 H 10 〕·0.4(C 5H 12 ) has been synthesized by the reaction of 〔NiCl 2(PPh 3) 2〕, closo 〔B 10 H 10 〕 2- and CH 3COSH in CH 2Cl 2 solution. It was recrystallized fr...The title compound 〔(PPh 3)(CH 3COS) 2NiB 10 H 10 〕·0.4(C 5H 12 ) has been synthesized by the reaction of 〔NiCl 2(PPh 3) 2〕, closo 〔B 10 H 10 〕 2- and CH 3COSH in CH 2Cl 2 solution. It was recrystallized from n pentane/CH 2Cl 2 solution and its structure was determined by X ray diffraction analysis. The crystal is triclinic, space group P1, M r= 618.23, with a=10.049(1), b=12.638(2), c=14.077(2) , α=110.13(1), β=87.65(1), γ=96.01(1)°, V=1669.3(4) 3, D c =1.230 g/cm 3, Z=2, λ (Mo Kα )=0.71073 , μ =7.76 cm -1 , F (000)=642. The final refinement is converged with R =0.042 (5986 observed reflections with I≥2σ(I)), wR 2 =0.151. The cluster is a nido eleven vertex {NiB 10 } cage with the Ni atom in the open NiB 4 face. Cyclizations resulting in two five membered rings, Ni(7)-S(1)-C(1)-O(1)-B(2) and Ni(7)-S(2)-C(2)-O(2)-B(3), have occurred.展开更多
Triphenylphosphine coupled with trichloroacetamide was determined to be an effective reagent for the conversion of 2,3,4,6-tetra-O-benzyl-D-glucopyranose as a glycosyl hemiacetal to the corresponding glycosyl chloride...Triphenylphosphine coupled with trichloroacetamide was determined to be an effective reagent for the conversion of 2,3,4,6-tetra-O-benzyl-D-glucopyranose as a glycosyl hemiacetal to the corresponding glycosyl chloride in excellent yield under mild and neutral conditions. Subsequently, the glycosyl chloride was reacted with alcohol or glycosyl acceptors in the presence of zinc（ll） bromide and molecular sieve 5 A to afford the corresponding glycosides in high yields and a-selectivity. This practical and convenient protocol can be utilized for the one-pot glycosylation of glycosyl hemiacetals.展开更多
A series of phosphine oxide-functionalized polyfluorene derivatives,PFH-PO-40-1 (P1),PFH-PO-20-1 (P2),PFH-PO-10-1 (P3),and PFH-PO-1-1 (P4),were prepared via a palladium-mediated Suzuki cross-coupling reaction.The stru...A series of phosphine oxide-functionalized polyfluorene derivatives,PFH-PO-40-1 (P1),PFH-PO-20-1 (P2),PFH-PO-10-1 (P3),and PFH-PO-1-1 (P4),were prepared via a palladium-mediated Suzuki cross-coupling reaction.The structures and purities of all polymers were fully characterized by 1H and 13C NMR,UV-vis and photoluminescent spectroscopy,gel permeation chromatography,and TGA/DSC.Their emission features showed single broad peaks at about 445 nm in film,compared with those in dilute solutions,which might be caused by some degree of aggregation in the excited states of the backbones.The best electroluminescence (EL) performance of these polymers with configuration of ITO/PEDOT:PSS/Polymer/Alq3/LiF/Al was obtained from P1 (current efficiency was 4.2 Cd/A at 6V).展开更多
Four metallodithiolene complexes[4,8-bis(octyloxy)-1,3,5,7-tetrathia]?di[1,1′-bis(diphenylphosphino)ferrocene?palladium(II)](3),[4,8-bis(octyloxy)-1,3,5,7-tetrathia]di[1,3-bis(diphenylphosphino)propane?nickel(II)](4)...Four metallodithiolene complexes[4,8-bis(octyloxy)-1,3,5,7-tetrathia]?di[1,1′-bis(diphenylphosphino)ferrocene?palladium(II)](3),[4,8-bis(octyloxy)-1,3,5,7-tetrathia]di[1,3-bis(diphenylphosphino)propane?nickel(II)](4),[4,8-bis(octyloxy)-1,3,5,7-tetra-thia]?[1,1′-bis(diphenylphosphino)ferrocene?palladium(II)]?[1,3-bis(diphenylphosphino)propane·nickel(II)](5)and di[4,8-bis(octyloxy)-1,3,5,7-tetrathia]?[1,1′-bis(diphenylphosphino)ferrocene?palladium(II)]?nickel(II)(6)were synthesized and the near-infrared(NIR)electrochromic properties were studied.The spectroelectrochemical spectra and the electrochromic parameters such as optical contrast,switching time,optical density change,electrochromic efficiency and optical attenuation of complexes 3–6 were investigated in detail.The symmetric binuclear complex 4 showed relatively high electrochromic efficiency of63.0 and 75.4 cm^2/C both in the two oxidation states.The complexes exhibited excellent electroactive/electrochromic stability characterized by chronoamperometry(>4000 cyclic switches).展开更多
基金supported by the National Natural Science Foundation of China(21473058,21273077)~~
文摘The neutral palladium（Ⅱ） complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-imidazolyl]dichloropalladium（Ⅱ）（1A） ligated by thiazolylimidazolyl-based phosphine（L1） in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-3-methylimidazolium]dichloropalladium（Ⅱ） trifluoromethanesulfonate（2A） ligated by thiazolylimidazolium-based phosphine（L2） after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.
文摘C50H46OP4ClRh, RhCl(dppm)2 · H2O, Mr = 922. 2, monoclinic, P21/2, a=10. 532(3), b=22.574(8), c=18. 641(8) A, β=93. 41(3)°, V = 4424 (3) A3, Z = 4, Dc=1. 386 g. cm-3, λ(MoKα) = 0. 71073A , F(000) = 1904. The structure was determined by direct methods and difference Fourier syntheses and refined by full-matrix least-squares to final R = 0. 037 and Rw = 0. 036 for 3432 (F> 6. 0σ(F) ) observed reflections. The structure of the title compound contains RhCl-(dppm)2 and non-coordinated H2O molecules. The rhodium atom is coordinated by one chlorine atom and four phosphorus atoms of two DPPM ligands forming a tetragonal pyramidal configuration.
文摘The title compound 〔(PPh 3)(CH 3COS) 2NiB 10 H 10 〕·0.4(C 5H 12 ) has been synthesized by the reaction of 〔NiCl 2(PPh 3) 2〕, closo 〔B 10 H 10 〕 2- and CH 3COSH in CH 2Cl 2 solution. It was recrystallized from n pentane/CH 2Cl 2 solution and its structure was determined by X ray diffraction analysis. The crystal is triclinic, space group P1, M r= 618.23, with a=10.049(1), b=12.638(2), c=14.077(2) , α=110.13(1), β=87.65(1), γ=96.01(1)°, V=1669.3(4) 3, D c =1.230 g/cm 3, Z=2, λ (Mo Kα )=0.71073 , μ =7.76 cm -1 , F (000)=642. The final refinement is converged with R =0.042 (5986 observed reflections with I≥2σ(I)), wR 2 =0.151. The cluster is a nido eleven vertex {NiB 10 } cage with the Ni atom in the open NiB 4 face. Cyclizations resulting in two five membered rings, Ni(7)-S(1)-C(1)-O(1)-B(2) and Ni(7)-S(2)-C(2)-O(2)-B(3), have occurred.
文摘Triphenylphosphine coupled with trichloroacetamide was determined to be an effective reagent for the conversion of 2,3,4,6-tetra-O-benzyl-D-glucopyranose as a glycosyl hemiacetal to the corresponding glycosyl chloride in excellent yield under mild and neutral conditions. Subsequently, the glycosyl chloride was reacted with alcohol or glycosyl acceptors in the presence of zinc（ll） bromide and molecular sieve 5 A to afford the corresponding glycosides in high yields and a-selectivity. This practical and convenient protocol can be utilized for the one-pot glycosylation of glycosyl hemiacetals.
基金supported by the National Basic Research Program of China (2006CB921602 and 2009CB623601)National Natural Science Foundation of China,and Hewlett Packard Company
文摘A series of phosphine oxide-functionalized polyfluorene derivatives,PFH-PO-40-1 (P1),PFH-PO-20-1 (P2),PFH-PO-10-1 (P3),and PFH-PO-1-1 (P4),were prepared via a palladium-mediated Suzuki cross-coupling reaction.The structures and purities of all polymers were fully characterized by 1H and 13C NMR,UV-vis and photoluminescent spectroscopy,gel permeation chromatography,and TGA/DSC.Their emission features showed single broad peaks at about 445 nm in film,compared with those in dilute solutions,which might be caused by some degree of aggregation in the excited states of the backbones.The best electroluminescence (EL) performance of these polymers with configuration of ITO/PEDOT:PSS/Polymer/Alq3/LiF/Al was obtained from P1 (current efficiency was 4.2 Cd/A at 6V).
基金the National Natural Science Foundation of China (21134005, 21474102, 21474105)the Natural Science and Engineering Research Council of Canada
文摘Four metallodithiolene complexes[4,8-bis(octyloxy)-1,3,5,7-tetrathia]?di[1,1′-bis(diphenylphosphino)ferrocene?palladium(II)](3),[4,8-bis(octyloxy)-1,3,5,7-tetrathia]di[1,3-bis(diphenylphosphino)propane?nickel(II)](4),[4,8-bis(octyloxy)-1,3,5,7-tetra-thia]?[1,1′-bis(diphenylphosphino)ferrocene?palladium(II)]?[1,3-bis(diphenylphosphino)propane·nickel(II)](5)and di[4,8-bis(octyloxy)-1,3,5,7-tetrathia]?[1,1′-bis(diphenylphosphino)ferrocene?palladium(II)]?nickel(II)(6)were synthesized and the near-infrared(NIR)electrochromic properties were studied.The spectroelectrochemical spectra and the electrochromic parameters such as optical contrast,switching time,optical density change,electrochromic efficiency and optical attenuation of complexes 3–6 were investigated in detail.The symmetric binuclear complex 4 showed relatively high electrochromic efficiency of63.0 and 75.4 cm^2/C both in the two oxidation states.The complexes exhibited excellent electroactive/electrochromic stability characterized by chronoamperometry(>4000 cyclic switches).
