JOURNAL OF CATALYSIS
·
2019
·
IF 7.723
Da Yang,Lei Liu,Dong-Liang Wang,Yong Lu,Xiao-Li Zhao,Ye Liu
A series of novel multi (bi-/tri-/tetra-)-dentate phosphines with good robustness against water and oxygen were synthesized and fully characterized. It was found that the developed ionic tri-dentate phosphine ( L2′ ) enabled Pd-catalyzed alkoxycarbonylation of alkynes most efficiently while H 2 O was used as an additive instead of acid. As for L2′ , its unique steric configuration with two types of potential P-P chelation modes (P⋯P distance of 4.31 Å and 4.36 Å respectively) to Pd-centre rendered the corresponding Pd-catalyst high activity and good stability for alkoxycarbonylation of alkynes. The in situ FT-IR analysis also verified that the formation and stability of Pd–H active species were greatly facilitated with the presence of L2′ as well as H 2 O additive. In addition, as an ionic phosphine, L2′ based PdCl 2 (MeCN) 2 system immobilized in RTIL of [Bmim]NTf 2 could be recycled for 7 runs without obvious activity loss or metal leaching.
研究领域:
有机化学
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催化化学
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产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2019
·
IF 7.723
Huan Liu,Lei Liu,Wen-Di Guo,Yong Lu,Xiao-Li Zhao,Ye Liu
The complexation of IrCl 3 ⋅3H 2 O with the electron-deficient phosphines ( L1 - L6 ) respectively afforded a bi-functional catalyst possessing the dual functions of transition metal complex (Ir III -P) and Ir III -Lewis acid for tandem hydroformylation-acetalization of olefins. The best result was obtained over L5 -based IrCl 3 ⋅3H 2 O catalytic system which corresponded to 97% conversion of 1-hexene along with 92% selectivity to the target acetals free of any additive. The crystal structure of the novel Ir III -complex of Ir III -L4 indicated that the electron-deficient nature of the involved phosphine warranted Ir-center in +3 valence state without reduction, which served as the Lewis acid catalyst for the subsequent acetalization of the aldehydes as well. Moreover, as an ionic phosphine, L6 -based IrCl 3 ⋅3H 2 O system immobilized in RTIL of [Bmim]PF 6 could be recycled for 6 runs without the obvious activity loss or metal leaching.
研究领域:
化学
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催化化学
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有机合成
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产品关联
DOI
高影响因子
POLYMER SCIENCE SERIES B
·
2016
·Vol. 58
·期 5
·495-502
·
IF 0.737
Geng Jieting,Sun Yanjie,Hua Jing
Polyisoprene with relatively high content of 1,2/3,4 structure was synthesized using a novel catalyst system composed of MoO 2 Cl 2 supported by phosphorus ligand and Al(OPhCH 3 )( i -Bu) 2 as co-catalyst. The effects of phosphites, phosphates and phosphoric acid as ligands were investigated in the coordination polymerization of isoprene in the chosen catalyst system. The studied ligands significantly affected the catalytic activity of the Mo–Al catalytic active center without significant effect on the stereoselectivity. Mo(VI)-based catalyst system was proved to be highly effective in the polymerization of isoprene even at low [Al]/[Mo] ratio (10), affording polyisoprene with 1,2- and 3,4-% structural units in the range of 44.6–52.5%, high molecular weights M
n ~ 10 5 , and relatively broad molecular weight distributions ( M
w / M
n = 3.0–4.4). The effect of molar ratio of phosphorous ligand to Mo-catalyst on catalyst activity of isoprene polymerization was discussed, and the structures of Mo–phosphite complexes were preliminarily studied by IR.
研究领域:
材料科学
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催化化学
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DOI
高影响因子
Nature Communications
·
2022
·Vol. 13
·期 1
·1-7
·
IF 17.694
Song Yongbo,Li Yingwei,Zhou Meng,Li Hao,Xu Tingting,Zhou Chuanjun,Ke Feng,Huo Dayujia,Wan Yan,Jie Jialong,Xu Wen Wu,Zhu Manzhou,Jin Rongchao
The growth of nanoparticles along one or two directions leads to anisotropic nanoparticles, but the nucleation (i.e., the formation of small seeds of specific shape) has long been elusive. Here, we show the total structure of a seed-sized Au 56 nanoprism, in which the side Au{100} facets are surrounded by bridging thiolates, whereas the top/bottom {111} facets are capped by phosphine ligands at the corners and Br − at the center. The bromide has been proved to be the key to effectively stabilize the Au{111} to fulfill a complete face-centered-cubic core. In femtosecond electron dynamics analysis, the non-evolution of transient absorption spectra of Au 56 is similar to that of larger-sized gold nanoclusters ( n > 100), which is ascribed to the completeness of the prismatic Au 56 core and an effective electron relaxation pathway created by the stronger Au-Au bonds inside. This work provides some insights for the understanding of plasmonic nanoprism formation.
研究领域:
材料科学
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纳米技术
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物理化学
✓ 已验证
DOI
PubMed
高影响因子
RSC Advances
·
2019
·Vol. 9
·期 24
·13476-13485
·
IF 3.049
Fan Zhang,Chuting Yang,Yi Li,Min Chen,Sheng Hu,Haiming Cheng
P,P-bis (2-oxooxazolidin-3-yl)-N-(3-(triethoxysilyl)propyl)phosphinic amide (APTES-BOP)-modified SBA-15 (SBA-15-BOP) was prepared by a post-synthesis grafting method for the removal of anionic azo dyes from aqueous solutions. The properties of the prepared adsorbent were characterized by PXRD, FT-IR, SEM, TEM, nitrogen sorption, and elemental analysis. Adsorption equilibrium and adsorption kinetic studies demonstrated that the experimental data fitted well with the Langmuir isotherm model and pseudo-second-order model. According to Langmuir fitting, SBA-15-BOP showed high adsorption capacity for CR and RR2 dyes, with the maximum adsorption capacities of 518.1 mg g−1 and 253.8 mg g−1, respectively. The thermodynamic study indicated that the adsorption processes of CR and RR2 dyes on SBA-15-BOP were spontaneous and exothermal. The prepared SBA-15-BOP can be a promising adsorbent for the removal of anionic dyes from aqueous solutions.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
·
2015
·
IF 3.615
Heng Zhang,Yong-Qi Li,Peng Wang,Yong Lu,Xiao-Li Zhao,Ye Liu
The effect of positive charges in the diphosphino-imidazolium salts of L2 was investigated in terms of coordinating character, structures of corresponding Ir-complexes and catalysis for hydroformylation. It was found that the involved positive charges exhibited strong electron-withdrawing effect on the neighbored phosphine fragment, rendering L2 more π -acceptor ability than the corresponding neutral counterpart of L1 . Consequently, the changed coordinating ability of L1 and L2 led to the variety in the structures and components for the Ir-complexes ( Ir-L1a , Ir-L1b , Ir-L2a , and Ir-L2b ). The complexation of L2 with Ir(acac)(CO) 2 led to a novel five-coordinate Ir(II)-complex of Ir-L2a chelated by a PCC (phosphine–carboanion–carbene) pincer in tripodal mode, whereas the complexation of L1 with Ir(acac)(CO) 2 led to a four-coordinate square-planar Ir(I)-complex of Ir-L1a chelated by a PCP (phosphine–carboanion–phosphine) pincer. In addition, the different catalytic performances of these Ir-complexes ligated by L1 and L2 for hydroformylation of olefins were investigated.
研究领域:
化学
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催化化学
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产品关联
DOI
高影响因子
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
·
2014
·Vol. 2014
·期 6
·975-985
·
IF 2.965
Jing Zhang,Yongyong Wang,Xiaoli Zhao,Ye Liu
Graphical The ionic palladium complexes 1A – 4A ligated by imidazolium-based-phosphanes were prepared and shown, by single-crystal X-ray diffraction analyses, to be composed of Pd II -centered square-planar cations and OTf – counteranions. The complexes were tested as precatalysts for the homogeneous carbonylative Sonogashira coupling of aryl iodides with phenylacetylene. The stable ionic Pd II complexes 1A – 4A were synthesized through the complexation of PdCl 2 (MeCN) 2 with the phosphane-functionalized ionic liquids (FILs) 1 – 4 with π-acceptor character. Single-crystal X-ray diffraction analyses showed that 1A – 4A were all composed of Pd II -centred square-planar cations and triflate (OTf – , CF 3 SO 3 – ) counteranions. The complex cations in 1A – 3A possessed structural similarity to trans -PdCl 2 (PPh 3 ) 2 . The cation in 4A was a new Pd II -centered planar complex ligated by the phosphane–carbon anion–carbene (PCC) pincer in a tripodal manner. The stabilities of 1A – 4A were improved due to the intensive π-backbonding interaction between the Pd and P atoms. When complexes 1A – 4A were used as precatalysts for homogeneous carbonylative Sonogashira coupling of PhI with phenylacetylene free of CuI, 1A – 3A exhibited excellent catalytic behaviour with a TON of up to 1700 at a CO pressure of 0.5 MPa and moderate temperature of 100 °C, whereas 4A exhibited poor activity towards the transformation of PhI due to the high stability of 4A . The recycling experiments of 3A in [Bpy]BF 4 (as a solvent) indicated that 3A could be recycled for 5 runs with neither activity loss nor metal leaching into the organic phase. Complex 3A also proved to be a general precatalyst for the carbonylative Sonogashira couplings of a wide range of aryl iodides with phenylacetylene. The selectivity of the desired carbonylation product depended more on electronic effects than the steric effects of the substituents of the aryl iodides.
研究领域:
有机化学
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催化化学
✓ 已验证
DOI
高影响因子
INORGANICA CHIMICA ACTA
·
2021
·
IF 2.545
Dan Zheng,Ting-Hong Huang,Cheng Luo,Jing Tang
Three dinuclear Cu(I) complexes, [Cu 2 (pnd)(PPh 3 ) 4 ](BF 4 ) 2 (1) , [Cu 2 (pnd)(dppp) 2 ] (BF 4 ) 2 (2) , and [Cu 2 (pnd)(DPEphos) 2 ](BF 4 ) 2 (3) (PPh 3 = triphenylphosphine , dppp = 1, 3-bis (diphenylphosphino)propane, DPEphos = bis(2-diphenylphosphinophenyl)ether, pnd = N , N ’-bis (pyridin-2-ylmethylene)naphthyl-1, 5-diimine), have been prepared and characterized by IR, 1 H NMR, 31 P NMR, 13 C NMR, XRD , elemental analysis and X-ray crystal structure analysis. The structural analysis reveals that the flexible pnd in 1 – 3 acts in a trans bridging coordination mode to connect two Cu + ions, forming a S-shape conformation, while each of Cu (I) ion is four-coordinate N2P2, adopting a distorted-tetrahedral geometry. DFT calculations show that the HOMOs of complexes 1 – 3 are primarily located on the copper d -orbital and the phosphine ligand, together with a specific contribution of pnd, while LUMOs are mostly composed of pnd with admixed Cu(I) d-orbital character. Corresponding calculations of atomic charges indicate that the charge of the copper atom in complexes 1 – 3 is below + 1, while the total charges of the coordinated atoms are 0.743–0.786. Moreover, the solid-state emission spectra of complexes 1 – 3 show the existence of broad emission bands at 350–550 nm.
研究领域:
无机化学
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理论化学
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材料科学
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DOI
高影响因子
HETEROCYCLIC COMMUNICATIONS
·
2023
·Vol. 29
·期 1
·
IF 2.3
Mingyu Zhang,Yuqi Tang,Rui Xu,Dong Yan,Shuangping Xu,Yanqing Qu,Jingyu Xu,Hongge Jia
Due to the chemical properties of Group VIII transition metals and their importance in catalytic processes, the reactions of rhodium and its neighboring organic complexes have received much attention as model systems. In the present experiments, we successfully prepared two new rhodium complexes named [Rh(cod)(TTP)Cl] and [Rh(cod)(CDP)Cl] using tri( o -tolyl)phosphine and clohexyldiphenylphosphine as ligands, respectively, and the proofs of their structures were completed using 1 H NMR and 13 C NMR. Subsequently, it was applied to the polymerization reaction of phenylacetylene (PA), and the effects of different solvents, time, and temperature on the yield and molecular weight of the polymerization reaction products were discussed. The experimental results show that both complexes can play a catalytic role in the polymerization of PA. From the point of view of polymer molecular weight, the best reaction conditions for both catalysts were 3 h at 20°C in THF solvent (molecular weight up to 2.40 × 10 5 ). From the point of view of yield, the best reaction conditions for both catalysts were 4 h at 35°C in THF solvent (yield up to 89.2%).
研究领域:
化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2019
·
IF 7.723
Kaikai Liu,Hongliang Xin,Minghan Han
The phosphorus (III) ligands were crucial for the further improvement of homogeneous nickel catalysts that were employed in the isomerization of 2-methyl-3-butenenitrile (2M3BN) to 3-pentenenitrile (3PN). The catalytic behavior of 1,4-bis(diphenylphosphino)butane (dppb 1 )Ni complex was improved in cumene and the conversion of 2M3BN showed zero-order kinetic. The mechanism behind the isomerization was amended and the density functional theory (DFT) calculations suggested that the reductive elimination step forming 3PN was kinetically relevant in catalytic cycles. An optimal bite angle of nickel-diphosphine complex around 104.7° provided excellent catalytic performance. The key factors governing isomerization were unraveled. The steric effect determined the reactivity, while the electronic effect governed the selectivity of the isomerization reaction. The bite angle – a vital descriptor – would associate with the steric and electronic effects of diphosphines. These structure-activity relationships provided important guidance for ligand design in the isomerization of 2M3BN.
研究领域:
化学
·
催化科学
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
·
2013
·
IF 3.187
Sheng-Jie Chen,Yong-Yong Wang,Wei-Min Yao,Xiao-Li Zhao,Giang VO-Thanh,Ye Liu
A novel ionic complex with insensitivity to moisture and air, bis-[1-butyl-2-diphenylphosphanyl-3-methylimidazolium]tetrachloridorhodium(III) hexafluorophosphate ( 1A ), has been synthesized and fully characterized. The single-crystal X-ray diffraction analysis shows that 1A is composed of the Rh(III)-complex cation and the counter-anion of PF 6 − . The complex cation has highly symmetrical Rh III -centered octahedron geometry with four Cl atoms in the equatorial plane and two imidazolium-substituted phosphine ligands in the axial position. The catalytic performance of 1A , which could be tailored by the ligands and the solvents, was investigated toward the biphasic hydroformylation of 1-octene. It was found that the presence of the hemilabile hybrid P,N-ligand of 3 (1-(2′-piperid-1′-yl-ethyl)-2-diphenylphosphino-3-methylimidazolium hexafluorophosphate), as a kind of ligand-functionalized ionic liquids (ILs), could dramatically spur the catalytic activity of 1A . The use of the RTIL of [PEmim]BF 4 (1-(2′-piperid-1′-yl-ethyl)-3-methylimidazolium tetrafluoroborate) as the solvent not only fulfilled the efficient biphasic hydroformylation of 1-octene, but also guaranteed the successful recovery and recycling of the ionic compositions of 1A and 3 .
研究领域:
化学
·
催化反应
✓ 已验证
DOI
高影响因子
Chemistry-An Asian Journal
·
2025
·
IF 3.3
Zhuoyuan Li,Chuanjun Zhou,Kaiyang Kuang,Jiahao Liu,Shuang Chen,Shan Jin,Manzhou Zhu
Surface ligands significantly influence the optical properties and stability of metal nanoclusters. In this study, we synthesized [Pt1Ag31(S-Adm)16(DPPM)3(DPPMO)Cl3](SbF6)4 (Pt1Ag31-DPPMO). Compared to [Pt1Ag31(S-Adm)16(DPPM)3Cl3](SbF6)4 (Pt1Ag31), the introduction of secondary phosphine oxide ligand, DPPMO, results in Pt1Ag31-DPPMO exhibiting enhanced photoluminescent properties in both solution and solid states, as well as improved stability and electron-withdrawing ability. This work presents a novel strategy to regulate the properties of metal nanoclusters, especially enhancing photoluminescence performance and stability, through the incorporation of secondary phosphine oxide ligand.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）