JOURNAL OF MOLECULAR STRUCTURE
·
2021
·
IF 3.196
Ting-Hong Huang,Cheng Luo,Dan Zheng,Jing-Yang Tan,Yong Liu,Jing Tang
Based on α- and β-naphthylamine, two new diphosphines, N,N-bis((diphenylphos phino)methyl)naphthalen-1-amine ( 1 ) and N,N-bis((diphenylphosphino)methyl)naphthalene -2-amine ( 2 ), have been prepared and characterized by IR, 1 H NMR, 31 P NMR, TG, UV-Vis, XRD and X-ray crystal structure analysis. Structural analysis shows that the two Ph 2 PCH 2 - groups in 1 and 2 are disposed in an anti configuration, and the change of the position of the (Ph 2 PCH 2 ) 2 N-group on the naphthalene moiety results in different spatial configurations of the two Ph 2 P- groups and different weak interactions, such as C-H … π and π–π interactions. DFT studies show that the composition of the HOMOs for 1 and 2 are almost the same (the naphthyl group with admixed N and P atoms), but the ingredients of the LUMOs for 1 are different from that for 2, coinciding with the change of Mülliken atomic charges . Moreover, the emission spectra show that the emissions of complexes 1 and 2 in acetonitrile solution are not similar to those of solid-state samples.
研究领域:
有机化学
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计算化学
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材料科学
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DOI
高影响因子
Catalysis Science & Technology
·
2015
·Vol. 6
·期 11
·3854-3861
·
IF 5.426
Peng Wang,Huan Liu,Yong-Qi Li,Xiao-Li Zhao,Yong Lu,Ye Liu
A series of ionic phosphonium-based aminophosphines L1–L3 were prepared and fully characterized, in each of which the involved bifunctional moieties of the phosphine fragment and Lewis acidic phosphonium were linked together by stable chemical bonds and bridged by one N-atom. The molecular structure of the L2-ligated Rh-complex (Rh-L2) indicated that such bifunctionalities were well retained without incompatibility problems. Investigations on co-catalysis over L1–L3 showed that L3 exhibited the best sequential catalysis for both hydroformylation and acetalization. The phosphine fragment in L3 was responsible for hydroformylation together with the Rh-complex and the phosphonium acted as the Lewis acidic catalyst in charge of acetalization. The L3–Rh(acac)(CO)2 system also exhibited good generality to hydroformylation–acetalization of a wide range of olefins in different alcohols.
研究领域:
有机化学
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催化化学
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DOI
高影响因子
CHINESE JOURNAL OF CHEMISTRY
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2015
·Vol. 33
·期 5
·578-582
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IF 1.578
Minting Liang,Xiaofeng Xia,Xiang Liu,Hexing Li
In the presence of the inexpensive and non-toxic polymethylhydrosiloxane, the combination of copper(II) acetate and a chiral diphosphine displayed high catalytic efficiency in the asymmetric hydrosilylation of a series of aromatic ketones in air atmosphere and at room temperature. ( R )-1-Arylethanols were obtained with up to 99% yield and 93% enantiomeric excess. Meanwhile, the electron effect and steric hindrance of substituents on the aromatic ring had an interesting influence on both the yields and enantioselectivities. Furthermore, a possible mechanism was presented to explain the influence of some key factors on the reaction.
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
ORGANIC PROCESS RESEARCH & DEVELOPMENT
·
2014
·
IF 2.549
Liang Xu,Zhi-Hong Huang,Christian A. Sandoval,Lian-Quan Gu,Zhi-Shu Huang
A novel efficient asymmetric hydrogenation (AH) process was developed for the preparation of (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethanol (3), using a catalyst Ru/(4R,5R)-(+)-4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxoane-(R,R-Diop)-2R-(α-methylmethanamine)-4,7-dimethyl-1H-benzo[d]imidazole (R-D-Me-BIMAH) in toluene in the presence of potassium t-butoxide. Various hydrogenation parameters, such as ligand, solvent, and substrate-to-catalyst (S/C) ratio, were investigated. The hydrogenation was carried out for four times on a 5 kg scale at 30 atm and 25 °C with S/C of 20 000 with an enantiomeric excess of >89%.
研究领域:
有机化学
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催化化学
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DOI
高影响因子
Nanoscale
·
2022
·Vol. 14
·期 42
·15804-15811
·
IF 8.307
Qinzhen Li,Sha Yang,Jinsong Chai,Hui Zhang,Manzhou Zhu
Unraveling the rules governing the size regulation of nanoclusters is of great importance not only in fundamental research, but also in practical applications because of the high structure–property correlation in nanoclusters. Diphosphine-mediated size tailoring is recognized as a powerful method for modulating the size, configuration, and properties of nanoclusters, but the role of diphosphines in these size-controlled processes is still poorly understood due to a lack of systematic studies. Herein, using Au23(SR)16− as the template for modification, the factors influencing the size-modulation of nanoclusters by diphosphines were systematically investigated. It is revealed that by controlling the length of the diphosphines (from shorter to longer), Au21(SR)12L2+ (L = diphosphine) and Au22(SR)14L can be produced. Moreover, introducing a rigid group into the diphosphines can twist the structural framework or lead to the formation of a new surface motif configuration in the nanoclusters, forming twisted Au22(SR)14L and Au25(SR)16L2+. The size regulation of these nanoclusters enables fine-tuning of the optical properties, including the absorption wavelengths and photoluminescence emission intensity, affording an avenue for precise control of the physicochemical properties of nanoclusters for practical applications.
研究领域:
纳米材料科学
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配位化学
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物理化学
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产品关联
DOI
PubMed
高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Long-Gen Hu,Guo-Sheng Zhang,Guang-Hui Shi,Jian-Guo Qian,Hai-Jing Wang,Ye Liu
The Pd-catalyzed aminocarbonylation as well as hydroxycarbonylation of terminal alkynes was achieved with aid of a sulfonate-built-in zwitterionic phosphine ( L2 ), under acid-additive free condition. With L2 -Pd(OAc) 2 catalytic system, the terminal alkynes smoothly converted to the corresponding α,β -unsaturated carbonyl compounds (amides or carboxylic acids) in moderate to excellent isolated yields, with 100 % branched regio-selectivity. It was believed that L2 with the matched steric-demand and the bulit-in-SO 3 - -unit not only tuned the catalytic performance of Pd(OAc) 2 to activate CO and alkyne but also exhibited the synergetic activating ability towards the nucleophiles of (primary/secondary) amines or H 2 O via developing hydrogen-bond interaction, which facilitated the observed successful carbonylation. It means the developed L2 -Pd(OAc) 2 system could serve as a bifunctional catalyst.
研究领域:
有机化学
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催化化学
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配位化学
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合成化学
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物理有机化学
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产品关联
DOI
高影响因子
Materials
·
2025
·Vol. 18
·期 7
·1518
·
IF 3.2
Chengqi Liu,Zahir Abdalla,Xiaoqian Wang,Manrui Liu,Yanhui Jiao,Zisheng Tang,Qi Zhang,Yong Liu
Metal halide perovskite nanorods hold great promise for optoelectronic applications. However, they tend to undergo phase transitions due to the instability of the crystal phase under environmental conditions, leading to a rapid decline in the fluorescence efficiency. Here, we report a method in which trioctylphosphine (TOP) directly serves as both the surface ligand and solvent to synthesize highly stable α-CsPbI3nanorods (NRs). This approach produces monodisperse α-phase NRs with controlled sizes (1 μm and 150 nm in length, and an aspect ratio of 10:1), as confirmed by high-resolution transmission electron microscopy (TEM) and X-ray diffraction. The optimized NRs exhibit a high photoluminescence quantum yield of around 80%, as well as excellent environmental stability; after 15 days of storage, the photoluminescence quantum yield (PLQY) retention is 90%. Transient absorption spectroscopy shows that the carrier lifetime is extended to 23.95 ns and 27.86 ns, attributed to the dual role of TOP in defect passivation and hydrolysis suppression. This work provides a scalable paradigm for stabilizing metastable perovskite nanostructures through rational ligand selection, paving the way for durable perovskite-based optoelectronics.
研究领域:
材料科学
·
光学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF ORGANOMETALLIC CHEMISTRY
·
2023
·
IF 2.3
Yi-Fan Tan,Guang-Min Liang,Kun Zhou,Jiu-Yu Ji,Li-Ping Zhao
A new three-dimensional (3D) supramolecular compound, [Ag(dppe)(CF 3 COO)] n ( 1 ), was prepared by using Ag(I) as the silver source and dppe as the organic ligand through the self-assembly approach. The bridging dppe ligand makes compound 1 appear as a one-dimensional (1D) wavy chain consolidated by the intramolecular hydrogen bonds. Two adjacent 1D chains are expanded to a two-dimensional (2D) layer passing through the intermolecular C H···π interaction between the dppe ligands, and the 2D layers further weave into a 3D supramolecular structure via another intermolecular C H···π interactions between the dppe ligands. The precise structure of 1 was determined by single crystal X-ray diffractometer (SCXRD), and it was well-characterized by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis (TG) and differential thermogravimetry analysis (DTG), and UV–vis diffuse reflectance spectrum. In addition, the photocurrent response, electrochemistry characteristic and photodegradation of 1 were investigated. The degradation efficiency (82 %) of 1 as catalyst to degrade methylene blue (MB) was significantly higher than that without catalyst.
研究领域:
化学
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材料科学
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产品关联
DOI
高影响因子
RSC Advances
·
2023
·Vol. 13
·期 40
·27865-27872
·
IF 3.9
Fan Wang,Shuai Zhang,Congxia Xie,Xin Jin
Herein, based on the concept of integration of phosphine ligands and ionic liquids (ILs), a class of chiral phosphine-functionalized polyether ionic liquids (CPF-PILs) were synthesized by ion-exchange reaction between polyether imidazolium ILs and a phenyl-sulfonated (S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) chiral diphosphine ligand, and employed in the Ru-catalyzed homogeneous asymmetric hydrogenation of β-keto esters. The resulting CPF-PILs combined the dual functions of the chiral phosphine ligand and ILs, allowing efficient recovery and recycling of the chiral catalysts using only a catalytic amount of CPF-PILs. The effects of various factors, including the chiral catalyst structure, solvent properties, reaction temperature, hydrogen pressure, and hydrobromic acid dosage, on catalytic performance were thoroughly investigated, as well as the cycling stability and universality of the chiral catalysts were examined. The findings of the present study demonstrated that, under optimal reaction conditions, the model substrate methyl acetoacetate underwent quantitative conversion to methyl β-hydroxybutyrate with a 97% enantiomeric excess (ee). The chiral catalyst used in this process can be recycled up to 12 times and showed good applicability to structurally various β-keto esters. The present study presents a novel approach for using ILs in asymmetric hydrogenation reactions in an environmentally friendly manner.
研究领域:
化学
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催化
·
绿色化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
·
2024
·
IF 6.5
Tian-Hong Jing,Yi-Ying Zhuang,Xiao-Xin Zhang,Jian-Guo Qian,Xiao-Li Zhao,Yong Lu,Hai-Jing Wang,Ye Liu
The elaborate control of regioselectivity regulated by the involved ligands with specific structural skeleton and compositions is always demanded in alkoxycarbonylation of alkenes. Herein, a series of pinwheel-like tridentate phosphine ligands with rotatable flexibility ( L3 ) or hard rigidity ( L5–L7 ) were synthesized and characterized for the first time, in which the incorporated three PPh 2 -fragments are located at meta-positions of phenyl groups. It was proved that the tridentate phosphine of L3 with the flexible configuration favorably corresponded to the linear regioselectivity with l/b ratio of 98/2, whereas L7 with the rigid configuration absolutely did favor to the branched regioselectivity with l/b ratio of 1/99. The presence of the three PPh 2 -frgaments in L3 did contribute to the remarkable performance of L3 -Pd(TFA) 2 system in terms of activity, linear regioselectivity and stability, subjected to 10-run recycling uses in anti -Markovnikov’s methoxycarbonylation of styrene without activity loss and Pd-black precipitation. In comparison, although the optimal L7 -Pd(MeCN) 2 Cl 2 system could catalyze Markovnikov’s alkoxycarbonylation of alkenes to afford the branched esters with excellent regioselectivity in the fresh use, its stability was too poor to support the recycling experiments. L3 -Pd(TFA) 2 and L7 -Pd(MeCN) 2 Cl 2 catalytic systems were both applicable to a wide range of substrates in alkoxycarbonylation of alkenes to afford the target esters in the isolated yields of 41–91 %, with the well maintained divergent regioselectivity.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
Molecular Catalysis
·
2021
·
IF 5.062
Xiaoyuan Ma,Kunlong Yang,Jingchao Wang,Siyi Li,Tianyong Zhang,Shuang Jiang,Bin Li
Hydroquinone (HQ) and catechol (CAT) are the important raw materials in the chemical industry, which can be produced through a direct catalytic hydroxylation process using hydrogen peroxide as an oxidant. Herein, we report two novel diiron core complexes (μ-budt)Fe 2 (CO) 5 (DPEphos) (1) and (μ-budt)Fe 2 (CO) 5 (Xantphos) (2) supported by rigid heterocyclic xanthene-like diphosphine ligands which exhibit high selectivity and activity in phenol hydroxylation. The structures of complexes 1 and 2 were characterized by FT-IR, UV–vis, 1 H NMR, 31 P-NMR, X-ray crystallography, while the catalytic products were tested by using HPLC. The FT-IR and UV–vis spectra reveal that two diphosphine ligands exhibit similar impacts on the structure of parent complex (μ-budt)Fe 2 (CO) 6 [budt = SCH(CH 3 )CH 2 CH 2 )S]. Despite the similarity of ligands’ impact on the structure of the parent complex, the catalytic behavior was strongly influenced by the electronic and steric effects. The factors influencing the catalytic activity were optimized, including catalyst dosage, phenol/ H 2 O 2 molar ratio, reaction temperature, and time. Under the optimal conditions, 1 exhibits great catalytic performance with 57.7% phenol conversion and 49.6% DHB yield, both of which are remarkable. The mechanism of phenol hydroxylation using 1 as a catalyst was also proposed. Hydroxyl radicals (•OH) were generated in the catalytic reaction, as demonstrated by electron spin resonance (ESR).
研究领域:
化学
·
催化材料
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2020
·
IF 6.215
Zhiyin Xiao,Mookan Natarajan,Wei Zhong,Xiaoming Liu
In this work, four complexes of Co(II) and Ni(II), [Co( L 1 ) 2 (CH 3 CN)](ClO 4 ) 2 ( 1 ), [Ni( L 1 ) 2 ](ClO 4 ) 2 ( 2 ), [Co( L 2 ) 2 (CH 3 CN)](ClO 4 ) 2 ( 3 ) and [Ni( L 2 ) 2 ](ClO 4 ) 2 ( 4 ) were synthesized by reacting the perchlorate hydrate of M(II) (M = Co and Ni) with the ligands, Ph 2 PN(cyclohexyl)PPh 2 ( L 1 ) and Ph 2 PN(pyridin-2-ylmethyl)PPh 2 ( L 2 ), respectively. The complexes were fully characterized, and their absolute structures were determined using X-ray single crystallographic analysis. The cobalt complexes ( 1 and 3 ) exhibited two reductions in acetonitrile , one reversible reduction at about −0.65 V and the other at about −2.0 V at which catalytic reduction of proton was observed. The two reductions were assigned to Co(II) → Co(I) and Co(I) → Co(0) processes, respectively. The reduction of Ni(II) → Ni(I) was negatively shifted by about 300 mV compared to the cobalt analogues and the process showed two closely located reversible reductions due to geometric isomerization between the square planar ( Sp ) and tetrahedral ( Td ) geometries, of which the Td isomer was first reduced due to the lower energy level of its frontier orbitals . The second reduction of the Ni(II) complexes ( 2 and 4 ) was invisible in the potential range examined. Upon addition of acetic acid, it shifted positively by over 300 mV and showed catalysis on proton reduction. The shift was attributed to proton-coupled electron transfer (PCET) effect which was further enhanced by the pendant pyridyl group in ligand L 2 . The nickel complexes showed much higher activity than cobalt analogues in the catalysis on proton reduction and the pendant base group could synergistically enhance the activity of the complex ( 4 ).
研究领域:
无机化学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）