A novel thermoregulated phosphine ligand PhP(CHCHO)CH(n=22) was synthesized and used for the Rh-catalyzed hydroformylation of mixed Colefins in aqueous/organic biphasic system.Under the optimized conditions,pressure =...A novel thermoregulated phosphine ligand PhP(CHCHO)CH(n=22) was synthesized and used for the Rh-catalyzed hydroformylation of mixed Colefins in aqueous/organic biphasic system.Under the optimized conditions,pressure =5 MPa (H:CO=1:1),phosphine/Rh =13(molar ratio),reaction time =6 h and temperature =130℃,the conversion of Colefins and the yield of aldehyde are 99%and 94%,respectively.The catalyst retained in aqueous phase can be easily separated from the product-containing organic phase by simple phase separation and the catalytic activity remains almost constant after four consecutive cycles.展开更多
The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N- (CH2PPh2)2 (n=1,2,3) were prepared by a new and simple route under mild conditions in good yield; the palladium (II) complexes of the ligands...The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N- (CH2PPh2)2 (n=1,2,3) were prepared by a new and simple route under mild conditions in good yield; the palladium (II) complexes of the ligands 3a~c with 2:1 or 4:1 -PPh2 to Pd2+ molar ratio were also prepared and characterized .展开更多
A nickel(Ⅱ) complex containing both dithiolato and phosphine ligands, Ni_2(PPh_3)_2(edt)_2 (edt = SCH_2CH_2S^(2-)), has been prepared and characterized by X-ray diffration. The complex crystallizes in the triclinic s...A nickel(Ⅱ) complex containing both dithiolato and phosphine ligands, Ni_2(PPh_3)_2(edt)_2 (edt = SCH_2CH_2S^(2-)), has been prepared and characterized by X-ray diffration. The complex crystallizes in the triclinic system, space group P-1, with a = 10.693(3), b = 17.457 (6), c = 10.606 (3)A, α= 102.84(2), β = 96.49 (2), γ = 82.56(3)°; V = 1906.8 A^3; D_c = 1.439g.cm^(-3) for Z=2; the final con- ventional R was 0.052 based on 3338 observed reflections. Nickel atoms are linked by two sulfur atoms from two edt ligands with the Ni--Ni distance of 2.893 A, and each Ni atom is coordinated by one phosphorus atom and three sulfur atoms with a square-planar geometry, where the average: length of Ni--S bond is 2.180 A and Ni--P bond 2.188 A. The UV-Vis and ~1H NMR spectra have also been recorded.展开更多
In this paper,a series of optically active MeO-BIPHEP-type ligands,(S)-6,6′-dimethoxy-2,2’-bis(di-p-alkoxyphenylphosphine)- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects o...In this paper,a series of optically active MeO-BIPHEP-type ligands,(S)-6,6′-dimethoxy-2,2’-bis(di-p-alkoxyphenylphosphine)- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.展开更多
Effects on the recycling efficiency of thermoregulated phase-separable Rh/PETPP (P-[p-C6H4O(CH2CH2O)nH]3, N=3n) complex catalyst involved in hydroformylation of 1-decene are for the first time presented. It was found...Effects on the recycling efficiency of thermoregulated phase-separable Rh/PETPP (P-[p-C6H4O(CH2CH2O)nH]3, N=3n) complex catalyst involved in hydroformylation of 1-decene are for the first time presented. It was found that the loss of Rh is dependent greatly on the composition of phosphine ligand PETPP and the organic solvent employed in the reaction.展开更多
The bidentate phosphine oxide ligand 1,8-bis(diphenylphosphino) naphthalene oxide (NAPO) and its EuⅢ complex 1 Eu(TTA)3(NAPO) (TTA=2-thenoyltrifluoroacetonate) were chosen to study the effect of bidentate phosphine o...The bidentate phosphine oxide ligand 1,8-bis(diphenylphosphino) naphthalene oxide (NAPO) and its EuⅢ complex 1 Eu(TTA)3(NAPO) (TTA=2-thenoyltrifluoroacetonate) were chosen to study the effect of bidentate phosphine oxide ligand on the photophysical properties of the corresponding complex. The intramolecular energy transfer processes of 1 were studied. The investigation showed that with bidentate structure NAPO could suppress solvent-induced quenching by enforcing the ligand-ligand interaction and the rigidi...展开更多
To address the issue of hemilabile catalyst in olefin polymerization catalysis, a cyclizing strategy was used to construct novel N-bridged phosphine-carbonyl palladium and nickel catalysts, resulting in improvements o...To address the issue of hemilabile catalyst in olefin polymerization catalysis, a cyclizing strategy was used to construct novel N-bridged phosphine-carbonyl palladium and nickel catalysts, resulting in improvements on ethylene(co)polymerizations. The N-bridged phosphinecarbonyl Pd catalysts(Pd1-Pd5) and Ni catalysts(Ni1-Ni5) bearing five-to eight-membered-ring structures were designed and synthesized.Catalytic performance for ethylene(co)polymerization became better as the size of N-containing bridge increased. The seven-membered-ring bridged catalysts Pd4 and Ni4 exhibited the best performance in terms of catalytic activity, polymer molecular weight and incorporation of acrylates and acrylic acid. The better performance of these catalysts bearing larger-size bridges was tentatively attributed to the methyleneinduced higher electron density around nitrogen, which strenghtens the coordination of carbonyl group to metal center, and also to the steric effect offered by this cyclization. This work provides a new strategy to enhance hemilabile polymerization catalysts.展开更多
Four novel palladium((Ⅱ)) complexes coordinated by phosphorus atoms from both 3,5-disubstituted-1H- 1,2,4-diazaphospholes in monodentate fashion were developed as efficient catalyst for the Mizoroki- Heck reactio...Four novel palladium((Ⅱ)) complexes coordinated by phosphorus atoms from both 3,5-disubstituted-1H- 1,2,4-diazaphospholes in monodentate fashion were developed as efficient catalyst for the Mizoroki- Heck reaction of aryl halides with electron-deficient olefins. The coupling reaction of awl halide bearig different functional groups with olefin derivatives took place and the corresponding products were isolated in good to excellent yields under optimal conditions. The procedure exhibits good functional group tolerance and wide substrate scope. This Mizoroki-Heck reaction was further achieved using Pd(OAc)2 and 3,5-di-isopropyl-1H-1,2,4-diazaphospholes as combined catalyst, which provide the convenient and alternative method in organic synthesis展开更多
Cobalt-bis(dinitrogen)complexes[LCo(N_(2))_(2)]−(3,4)with simple and commercially available bidentate phosphine ligands(L:Cy_(2)PCH_(2)CH_(2)PCy_(2))were synthesized and structurally characterized.Further N2 functiona...Cobalt-bis(dinitrogen)complexes[LCo(N_(2))_(2)]−(3,4)with simple and commercially available bidentate phosphine ligands(L:Cy_(2)PCH_(2)CH_(2)PCy_(2))were synthesized and structurally characterized.Further N2 functionalization by treating the complex 3b with i Pr_(3)SiCl afforded the first structurally characterized cobalt diazenido complex 5.These complexes 3–5 were found to be effective catalysts for the transformation of N2 into N(SiMe_(3))_(3).The electronic structure of the cobalt diazenido complex 5 is supported by quantum computational calculations based on stateof-the-art energy decomposition analysis(EDA)in conjunction with the natural orbitals for chemical valence(NOCV)method.展开更多
The catalytic performance of Ni( η 5 Ind) 2 complex in the dimerization of propylene was studied in combination with an organoaluminum co catalyst, eventually in the presence of a phosphine ligand. The effects...The catalytic performance of Ni( η 5 Ind) 2 complex in the dimerization of propylene was studied in combination with an organoaluminum co catalyst, eventually in the presence of a phosphine ligand. The effects of the type of aluminum co catalyst and its relative amount, the nature of phosphine ligand and P/Ni ratio as well as the reaction temperature were examined. The results indicated that the nickel precatalyst exhibited high productivity for the propylene dimerization together with organoaluminum. It was likely to strongly modify the reactivity in the catalytic system when using phosphine ligand as additives, especially at the reaction temperature below 0 ℃. The catalytic system based on Ni( η 5 Ind) 2 complex displayed an extremely high productivity (TOF up to 169000 h -1 ) and a good regioselectivity to 2,3 dimethylbutenes (2,3 DMB) in dimers (66 4%) under proper reaction parameters.展开更多
基金the financial support from the Program for New Century Excellent Talents in University (No.NCET-07-0138)the Science and Technology Project in Universities from the Education Department of Liaoning Province(No.2008T233).
文摘A novel thermoregulated phosphine ligand PhP(CHCHO)CH(n=22) was synthesized and used for the Rh-catalyzed hydroformylation of mixed Colefins in aqueous/organic biphasic system.Under the optimized conditions,pressure =5 MPa (H:CO=1:1),phosphine/Rh =13(molar ratio),reaction time =6 h and temperature =130℃,the conversion of Colefins and the yield of aldehyde are 99%and 94%,respectively.The catalyst retained in aqueous phase can be easily separated from the product-containing organic phase by simple phase separation and the catalytic activity remains almost constant after four consecutive cycles.
文摘The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N- (CH2PPh2)2 (n=1,2,3) were prepared by a new and simple route under mild conditions in good yield; the palladium (II) complexes of the ligands 3a~c with 2:1 or 4:1 -PPh2 to Pd2+ molar ratio were also prepared and characterized .
基金Project supported partly by the National Naural Science Foundation of China the Provincial Science Fund of Fujian.
文摘A nickel(Ⅱ) complex containing both dithiolato and phosphine ligands, Ni_2(PPh_3)_2(edt)_2 (edt = SCH_2CH_2S^(2-)), has been prepared and characterized by X-ray diffration. The complex crystallizes in the triclinic system, space group P-1, with a = 10.693(3), b = 17.457 (6), c = 10.606 (3)A, α= 102.84(2), β = 96.49 (2), γ = 82.56(3)°; V = 1906.8 A^3; D_c = 1.439g.cm^(-3) for Z=2; the final con- ventional R was 0.052 based on 3338 observed reflections. Nickel atoms are linked by two sulfur atoms from two edt ligands with the Ni--Ni distance of 2.893 A, and each Ni atom is coordinated by one phosphorus atom and three sulfur atoms with a square-planar geometry, where the average: length of Ni--S bond is 2.180 A and Ni--P bond 2.188 A. The UV-Vis and ~1H NMR spectra have also been recorded.
基金the NSFC(No.20272037),the Doctor's Foundation of Education Ministry of China(No.20030610022)Foundation of Xihua University(No.R0723315) and(No.07ZA109) for the financial support of this work.
文摘In this paper,a series of optically active MeO-BIPHEP-type ligands,(S)-6,6′-dimethoxy-2,2’-bis(di-p-alkoxyphenylphosphine)- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.
基金The financial support of the National Natural Science Foundation of China (grant no. 29906001) and the Research Institute of Petroleum Processing China Petroleum & Chemical Corporation is gratefully acknowledged.
文摘Effects on the recycling efficiency of thermoregulated phase-separable Rh/PETPP (P-[p-C6H4O(CH2CH2O)nH]3, N=3n) complex catalyst involved in hydroformylation of 1-decene are for the first time presented. It was found that the loss of Rh is dependent greatly on the composition of phosphine ligand PETPP and the organic solvent employed in the reaction.
基金Project supported by the National Natural Science Foundation of China (90406021, 50903028)Science and Technology Bureau of Heilongjiang Province (QC08C10)
文摘The bidentate phosphine oxide ligand 1,8-bis(diphenylphosphino) naphthalene oxide (NAPO) and its EuⅢ complex 1 Eu(TTA)3(NAPO) (TTA=2-thenoyltrifluoroacetonate) were chosen to study the effect of bidentate phosphine oxide ligand on the photophysical properties of the corresponding complex. The intramolecular energy transfer processes of 1 were studied. The investigation showed that with bidentate structure NAPO could suppress solvent-induced quenching by enforcing the ligand-ligand interaction and the rigidi...
基金financial support from the National Natural Science Foundation of China (Nos. 22122110 ad 21871250)the Jilin Provincial Science and Technology Department Program (No. 20200801009GH)Shaanxi Provincial Natural Science Basic Research Program-Shaanxi Coal and Chemical Industry Group Co., Ltd. Joint Fund (No. 2019JLZ-02)。
文摘To address the issue of hemilabile catalyst in olefin polymerization catalysis, a cyclizing strategy was used to construct novel N-bridged phosphine-carbonyl palladium and nickel catalysts, resulting in improvements on ethylene(co)polymerizations. The N-bridged phosphinecarbonyl Pd catalysts(Pd1-Pd5) and Ni catalysts(Ni1-Ni5) bearing five-to eight-membered-ring structures were designed and synthesized.Catalytic performance for ethylene(co)polymerization became better as the size of N-containing bridge increased. The seven-membered-ring bridged catalysts Pd4 and Ni4 exhibited the best performance in terms of catalytic activity, polymer molecular weight and incorporation of acrylates and acrylic acid. The better performance of these catalysts bearing larger-size bridges was tentatively attributed to the methyleneinduced higher electron density around nitrogen, which strenghtens the coordination of carbonyl group to metal center, and also to the steric effect offered by this cyclization. This work provides a new strategy to enhance hemilabile polymerization catalysts.
基金Financial support from Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(No. 2015157)Teaching Reform Project of Shanxi Normal University(No. SD2014JGKT-52)Undergraduate Training Programs for Innovation and Entrepreneurship of Modern College of Arts and Sciences, Shanxi Normal University(No. WL2015CXCY-YJ-26)
文摘Four novel palladium((Ⅱ)) complexes coordinated by phosphorus atoms from both 3,5-disubstituted-1H- 1,2,4-diazaphospholes in monodentate fashion were developed as efficient catalyst for the Mizoroki- Heck reaction of aryl halides with electron-deficient olefins. The coupling reaction of awl halide bearig different functional groups with olefin derivatives took place and the corresponding products were isolated in good to excellent yields under optimal conditions. The procedure exhibits good functional group tolerance and wide substrate scope. This Mizoroki-Heck reaction was further achieved using Pd(OAc)2 and 3,5-di-isopropyl-1H-1,2,4-diazaphospholes as combined catalyst, which provide the convenient and alternative method in organic synthesis
基金supported by the Basic Science Center of Transformation Chemistry of Key Components of Air,National Natural Science Foundation of China(no.21988101)M.Z.acknowledges China Postdoctoral Science Foundation(no.2019M650294)+1 种基金L.Z.acknowledges the financial support from NSFC(nos.21973044 and 21703099)Natural Science Foundation of Jiangsu Province for Youth(no.BK20170964)。
文摘Cobalt-bis(dinitrogen)complexes[LCo(N_(2))_(2)]−(3,4)with simple and commercially available bidentate phosphine ligands(L:Cy_(2)PCH_(2)CH_(2)PCy_(2))were synthesized and structurally characterized.Further N2 functionalization by treating the complex 3b with i Pr_(3)SiCl afforded the first structurally characterized cobalt diazenido complex 5.These complexes 3–5 were found to be effective catalysts for the transformation of N2 into N(SiMe_(3))_(3).The electronic structure of the cobalt diazenido complex 5 is supported by quantum computational calculations based on stateof-the-art energy decomposition analysis(EDA)in conjunction with the natural orbitals for chemical valence(NOCV)method.
文摘The catalytic performance of Ni( η 5 Ind) 2 complex in the dimerization of propylene was studied in combination with an organoaluminum co catalyst, eventually in the presence of a phosphine ligand. The effects of the type of aluminum co catalyst and its relative amount, the nature of phosphine ligand and P/Ni ratio as well as the reaction temperature were examined. The results indicated that the nickel precatalyst exhibited high productivity for the propylene dimerization together with organoaluminum. It was likely to strongly modify the reactivity in the catalytic system when using phosphine ligand as additives, especially at the reaction temperature below 0 ℃. The catalytic system based on Ni( η 5 Ind) 2 complex displayed an extremely high productivity (TOF up to 169000 h -1 ) and a good regioselectivity to 2,3 dimethylbutenes (2,3 DMB) in dimers (66 4%) under proper reaction parameters.