The new complexes [Ru(NO)(PPh3)]2(h2-Cm)(m=60 1 or 70 2) have been prepared by heating a solution of C60(or C70) with [Ru(NO)2(PPh3)2] in toluene. They have been characterized by elemental analysis, IR, UV/VIS, XPS, ...The new complexes [Ru(NO)(PPh3)]2(h2-Cm)(m=60 1 or 70 2) have been prepared by heating a solution of C60(or C70) with [Ru(NO)2(PPh3)2] in toluene. They have been characterized by elemental analysis, IR, UV/VIS, XPS, 13C and 31P NMR spectroscopy. The photovaltaic effect for the new compounds has been studied.展开更多
A new ruthenium complex trans-RuCl2(COD)Py2 has been synthesized and characterized by elemental analysis, IR, IH NMR and single-crystal X-ray diffraction. Crystal data: trans- RuCl2(COD)Py2, Mr = 438.35, monoclin...A new ruthenium complex trans-RuCl2(COD)Py2 has been synthesized and characterized by elemental analysis, IR, IH NMR and single-crystal X-ray diffraction. Crystal data: trans- RuCl2(COD)Py2, Mr = 438.35, monoclinic, space group P21/c, a = 8.9116(9), b = 14.6175(15), c = 13.7582(14)A, β = 101.994(1)°, V= 1753.1(3)A^3, Z= 4, Dc= 1.661 g/cm^3, F(000)= 888,μ = 1.199 mm^-1, R = 0.0376 and wR = 0.0789 for 2492 observed reflections with I 〉 2σ(I).展开更多
A series of ruthenium azopyridine complexes have recently been investigated due to their potential cytotoxic activities against renal cancer (A498), lung cancer (H226), ovarian cancer (IGROV), breast cancer (MCF-7) an...A series of ruthenium azopyridine complexes have recently been investigated due to their potential cytotoxic activities against renal cancer (A498), lung cancer (H226), ovarian cancer (IGROV), breast cancer (MCF-7) and colon cancer (WIDR). Thus, in order to predict the cytotoxic potentials of these compounds, quantitative structure-activity relationship studies were carried out using the methods of quantum chemistry. Five Quantitative Structure Activity Relationship (QSAR) models were obtained from the determined quantum descriptors and the different activities. The models present the following statistical indicators: regression correlation coefficient R2 = 0.986 - 0.905, standard deviation S = 0.516 - 0.153, Fischer test F = 106.718 - 14.220, correlation coefficient of cross-validation = 0.985- 0.895 and = 0.010 - 0.001. The statistical characteristics of the established QSAR models satisfy the acceptance and external validation criteria, thereby accrediting their good performance. The models developed show that the variation of the free enthalpy of reaction , the dipole moment μ and the charge of the ligand in the complex Ql, are the explanatory and predictive quantum descriptors correlated with the values of the anti-cancer activity of the studied complexes. Moreover, the charge of the ligand is the priority descriptor for the prediction of the cytotoxicity of the compounds studied. Furthermore, QSAR models developed are statistically significant and predictive, and could be used for the design and synthesis of new anti-cancer molecules.展开更多
As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,ag...As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,agrochemical,material industrial and other chemical production.In this research,we demonstrated transformations of biomass-based ethyl levulinate(EL)into GVL and pyrrolidones by using heterogeneous catalysts(CNT-Ru-1)with N-heterocyclic carbene ruthenium(NHC-Ru)complex grafted on multi-walled carbon nanotube(CNT).The Ru catalyst showed high efficiency on EL hydrogenation to GVL with both EL conversion and GVL yield exceeding 99%.Moreover,the Ru catalyst readily promoted reductive amination of EL in the presence of various amines for pyrrolidone synthesis.Finally,the Ru catalyst was also applicable to hydrogenation of various carbonyl compounds for the synthesis of the corresponding alcohols with excellent catalytic performance.The research provides insight for heterogenizing the homogeneous noble metal-based catalysts with high catalytic active for biomass-based transformations.展开更多
Three half-sandwich ruthenium(II) p-cymene complexes containing naphthalenebased Schiff base ligands [Ru(p-cymene)LCl](2 a~2 c) have been synthesized and characterized. Both Schiff-base ligands and ruthenium co...Three half-sandwich ruthenium(II) p-cymene complexes containing naphthalenebased Schiff base ligands [Ru(p-cymene)LCl](2 a~2 c) have been synthesized and characterized. Both Schiff-base ligands and ruthenium complexes were fully characterized by ^1H and ^13C NMR spectra, mass spectrometry and infrared spectrometry. The molecular structure of ruthenium complex 2 b was confirmed by single-crystal X-ray diffraction methods. For the complex: C(24H23ClN2ORu, Mr = 524.02, monoclinic, space group P21/c, a = 12.3888(4), b = 17.3296(6), c = 20.7744(7)A°, β = 92.8000(10)°, V = 4454.8(3) A°^3, Z = 8, Dc = 1.563 g/cm^3, μ = 0.936 mm^-1, F(000) = 2128, S = 1.154, the final R = 0.0309 and w R = 0.0703. Moreover, these ruthenium complexes are active catalysts for the hydrogenation of nitroarenes to aromatic anilines in the presence of sodium tetrahydroborate(NaBH4) reducing agent.展开更多
This paper summarizes our recent progress on the preparations and applications of electropolymerized thin films of redox-active ruthenium complexes.Thin films of vinyl-functionalized diruthenium or ruthenium-amine con...This paper summarizes our recent progress on the preparations and applications of electropolymerized thin films of redox-active ruthenium complexes.Thin films of vinyl-functionalized diruthenium or ruthenium-amine conjugated complexes are prepared by reductive electropolymerization.The resulting films are useful for multistate near-infrared electrochromism,ion sensing,and mimicking flip-flop and flip-flap-flop logic gates.The oxidative electropolymerization of diruthenium complexes with two distal triarylamine units affords electropolymers with an alternating diruthenium and tetraphenylbenzidine structural unit.The applications of the resulting films in multistate near-infrared electrochromism and resistive memory are discussed.展开更多
A new anionic dinuclear ruthenium complex bearing 1, 2-his(diphenylphosphinomethyl)benzene (BDPX) [NH2Et2][{RuCl (BDPX)}2(μ-Cl)3] (1) was synthesized and its structure was determined by an X-ray crystallo-graphic ana...A new anionic dinuclear ruthenium complex bearing 1, 2-his(diphenylphosphinomethyl)benzene (BDPX) [NH2Et2][{RuCl (BDPX)}2(μ-Cl)3] (1) was synthesized and its structure was determined by an X-ray crystallo-graphic analysis. This result indicated that complex 1 consisted of an anion dinuclear BDPX-Ru and a cationic di-ethylammonium. The crystal belonged to monoclinic system, C2/c space group with a=3.3552(7) nm, b= 1.8448(4) nm, c=2.4265(5) nm, β= 101.89(3)° and Z=8. The catalytic hydrogenation activities and selectivities of complex 1 for cinnamaldehyde were investigated.展开更多
Six bis-tridentate and two tris-bidentate cyclometalated ruthenium complexes with a 1,2,3-triazole-containing ligand have been prepared and characterized. Single-crystal X-ray analyses of complexes [(MeOptpy)Ru(Bud...Six bis-tridentate and two tris-bidentate cyclometalated ruthenium complexes with a 1,2,3-triazole-containing ligand have been prepared and characterized. Single-crystal X-ray analyses of complexes [(MeOptpy)Ru(Budtab)]-(PF6) and [(Mebip)Ru(Budtab)](PF6) are presented, where MeOptpy is 4′-p-methoxyphenyl-2,2′:6′,2"-terpyridine, Budtab is the 2-deprotonated form of 1,3-di(N-n-butyl-l,2,3-triazol-4-yl)benzene, and Mebip is bis(N-methyl-ben-zimidazolyl)pyridine. The electronic properties of these complexes are probed by spectroscopic and electrochemical analyses. Time-dependent density functional theory calculations have been performed to assist the assignment of the absorption spectra.展开更多
The reaction of a ruthenium carbide complex RuCl2(C:)(PCy3)2 with [H(Et2O)x]+[BF4]- at a molar ratio of 1:2 produced a two-core ruthenium carbene complex, {[RuCl(=CHPCy3)(PCy3)]2(μ-Cl)3}+·[BF4]-,...The reaction of a ruthenium carbide complex RuCl2(C:)(PCy3)2 with [H(Et2O)x]+[BF4]- at a molar ratio of 1:2 produced a two-core ruthenium carbene complex, {[RuCl(=CHPCy3)(PCy3)]2(μ-Cl)3}+·[BF4]-, in the form of a yellow-green crystalline solid in a yield of 94%. This two-core ruthenium complex is a selective catalyst for ring closing metathesis of unsubstituted terminal dienes. More importantly, no isomerized byproduct was observed for N-substrates when the two-core ruthenium complex was used as the catalyst at an elevated temperature(137 °C), indicating that the complex is a chemo-selective catalyst for ring closing metathesis reactions.展开更多
Ferrocene-terminated trans-Ru(dppm)2 (dppm=Ph2PCH2PPh2)-containing molecular wires with alligator clips were prepared. They are suitable for self-assembly on gold electrode to investigate the influence of metal incor...Ferrocene-terminated trans-Ru(dppm)2 (dppm=Ph2PCH2PPh2)-containing molecular wires with alligator clips were prepared. They are suitable for self-assembly on gold electrode to investigate the influence of metal incorporation on the electron transportation property of the molecular wires.展开更多
A near infrared (NIR) electrochromic attenu-ator based on a dinuclear ruthenium complex and polycrys-talline tungsten oxide was fabricated and characterized. The results show that the use of the NIR-absorbing rutheniu...A near infrared (NIR) electrochromic attenu-ator based on a dinuclear ruthenium complex and polycrys-talline tungsten oxide was fabricated and characterized. The results show that the use of the NIR-absorbing ruthenium complex as a counter electrode material can improve the device performance. By replacing the visible electrochromic ferrocene with the NIR-absorbing ruthenium complex, the optical attenuation at 1550 nm was enhanced from 19.1 to 30.0 dB and color efficiency also increased from 29.2 to 121.2 cm2/C.展开更多
The reaction between [Ru3(3-O)(-CH3CO2)6(py)2(MeOH)](PF6) (py = pyri- dine) and diphenyl-2-pyridyl-phosphine (PPh2py) gave the triruthenium cluster complex [RuIII3(3-O)(-CH3CO2)6(py)2(PPh2py)](PF6)CH2Cl2 (C40H44Cl2F6N...The reaction between [Ru3(3-O)(-CH3CO2)6(py)2(MeOH)](PF6) (py = pyri- dine) and diphenyl-2-pyridyl-phosphine (PPh2py) gave the triruthenium cluster complex [RuIII3(3-O)(-CH3CO2)6(py)2(PPh2py)](PF6)CH2Cl2 (C40H44Cl2F6N34O13P2Ru3) which was characterized by elemental analysis, IR, UV-Vis and 31P NMR spectroscopy, and X-ray single- crystal diffraction. The structure is of monoclinic, space group P21/n with a = 16.3896(1), b = 16.8773(2), c = 19.1438(2) ? b = 95.888(1), V = 5267.47(9) ?, Mr = 1324.83, Dc = 1.671 g/cm3, F(000) = 2636, m = 1.092 mm-1 and Z = 4. The final refinement gave R = 0.0508 and wR = 0.1111 for 6987 observed reflections (I > 2s(I)). Three Ru(III) atoms bridged by m3-oxo donor form an approximately isosceles triangle. The complex shows three quasireversible one- electron processes at E1/2 = 1.22 +0.03 and 1.20 V vs. Ag/AgCl.展开更多
A series of chiral secondary alcohols were easily prepared by means of asymmetric hydrogenation of prochiral aromatic ketones using a new((Rax)-BuP)/(R,R)-DPEN-Ru(Ⅱ) complex catalyst system.The hydrogenation ...A series of chiral secondary alcohols were easily prepared by means of asymmetric hydrogenation of prochiral aromatic ketones using a new((Rax)-BuP)/(R,R)-DPEN-Ru(Ⅱ) complex catalyst system.The hydrogenation of 2-methylacetophenone in n-butanol (t-BuOK/Ru =45.6/1,S/C = 500,20 atm.of H2,20℃,48 h) afforded(S)-1-(2'-methylphenyl)ethanol in 92%ee and〉99% conversion.展开更多
基金support of this work by the Doctor programe of Higher Education of China(No.98038410)Natural Science Foundation of Fujian(No.E0110001)Self-select program of Xiamen University.
文摘The new complexes [Ru(NO)(PPh3)]2(h2-Cm)(m=60 1 or 70 2) have been prepared by heating a solution of C60(or C70) with [Ru(NO)2(PPh3)2] in toluene. They have been characterized by elemental analysis, IR, UV/VIS, XPS, 13C and 31P NMR spectroscopy. The photovaltaic effect for the new compounds has been studied.
文摘A new ruthenium complex trans-RuCl2(COD)Py2 has been synthesized and characterized by elemental analysis, IR, IH NMR and single-crystal X-ray diffraction. Crystal data: trans- RuCl2(COD)Py2, Mr = 438.35, monoclinic, space group P21/c, a = 8.9116(9), b = 14.6175(15), c = 13.7582(14)A, β = 101.994(1)°, V= 1753.1(3)A^3, Z= 4, Dc= 1.661 g/cm^3, F(000)= 888,μ = 1.199 mm^-1, R = 0.0376 and wR = 0.0789 for 2492 observed reflections with I 〉 2σ(I).
文摘A series of ruthenium azopyridine complexes have recently been investigated due to their potential cytotoxic activities against renal cancer (A498), lung cancer (H226), ovarian cancer (IGROV), breast cancer (MCF-7) and colon cancer (WIDR). Thus, in order to predict the cytotoxic potentials of these compounds, quantitative structure-activity relationship studies were carried out using the methods of quantum chemistry. Five Quantitative Structure Activity Relationship (QSAR) models were obtained from the determined quantum descriptors and the different activities. The models present the following statistical indicators: regression correlation coefficient R2 = 0.986 - 0.905, standard deviation S = 0.516 - 0.153, Fischer test F = 106.718 - 14.220, correlation coefficient of cross-validation = 0.985- 0.895 and = 0.010 - 0.001. The statistical characteristics of the established QSAR models satisfy the acceptance and external validation criteria, thereby accrediting their good performance. The models developed show that the variation of the free enthalpy of reaction , the dipole moment μ and the charge of the ligand in the complex Ql, are the explanatory and predictive quantum descriptors correlated with the values of the anti-cancer activity of the studied complexes. Moreover, the charge of the ligand is the priority descriptor for the prediction of the cytotoxicity of the compounds studied. Furthermore, QSAR models developed are statistically significant and predictive, and could be used for the design and synthesis of new anti-cancer molecules.
基金the financial support from the National Natural Science Foundation of China(U1810111,51872124 and21676116)Natural Science Foundation of Guangdong Province,China(2018B030311010)+1 种基金the Fundamental Research Funds for the Central Universities(21617431)Key Laboratory of Biomass Chemical Engineering of Ministry of Education,Zhejiang University(2018BCE002)
文摘As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,agrochemical,material industrial and other chemical production.In this research,we demonstrated transformations of biomass-based ethyl levulinate(EL)into GVL and pyrrolidones by using heterogeneous catalysts(CNT-Ru-1)with N-heterocyclic carbene ruthenium(NHC-Ru)complex grafted on multi-walled carbon nanotube(CNT).The Ru catalyst showed high efficiency on EL hydrogenation to GVL with both EL conversion and GVL yield exceeding 99%.Moreover,the Ru catalyst readily promoted reductive amination of EL in the presence of various amines for pyrrolidone synthesis.Finally,the Ru catalyst was also applicable to hydrogenation of various carbonyl compounds for the synthesis of the corresponding alcohols with excellent catalytic performance.The research provides insight for heterogenizing the homogeneous noble metal-based catalysts with high catalytic active for biomass-based transformations.
基金National Natural Science Foundation of China(No.20774074 and 20674063)Specialized Research Fund for the Doctoral Program of Higher Education(No.20050736001).
文摘芳香并且烷基白酒用 Oxone 与高变换和选择在房间温度被氧化到相应的醛或酉同类?(2KHSO5 路 K HSO4 路 K 2SO4 ) 由钌建筑群 Quin-Ru-Quin 作为氧化剂催化(在哪儿奎因 = 8-hydroxyquinoline ) 。反应时间是很短的,建筑群的准备简单。
基金financially supported by the National Nature Science Foundation of China(21102004)Natural Science Foundation of Anhui Province(1708085MB44)the Natural Science Foundation of the Anhui Higher Education Institutions(KJ2016A845)
文摘Three half-sandwich ruthenium(II) p-cymene complexes containing naphthalenebased Schiff base ligands [Ru(p-cymene)LCl](2 a~2 c) have been synthesized and characterized. Both Schiff-base ligands and ruthenium complexes were fully characterized by ^1H and ^13C NMR spectra, mass spectrometry and infrared spectrometry. The molecular structure of ruthenium complex 2 b was confirmed by single-crystal X-ray diffraction methods. For the complex: C(24H23ClN2ORu, Mr = 524.02, monoclinic, space group P21/c, a = 12.3888(4), b = 17.3296(6), c = 20.7744(7)A°, β = 92.8000(10)°, V = 4454.8(3) A°^3, Z = 8, Dc = 1.563 g/cm^3, μ = 0.936 mm^-1, F(000) = 2128, S = 1.154, the final R = 0.0309 and w R = 0.0703. Moreover, these ruthenium complexes are active catalysts for the hydrogenation of nitroarenes to aromatic anilines in the presence of sodium tetrahydroborate(NaBH4) reducing agent.
基金the National Natural Science Foundation of China(Nos.21271176,21472196,21521062,and 21501183)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB 12010400)for funding support
文摘This paper summarizes our recent progress on the preparations and applications of electropolymerized thin films of redox-active ruthenium complexes.Thin films of vinyl-functionalized diruthenium or ruthenium-amine conjugated complexes are prepared by reductive electropolymerization.The resulting films are useful for multistate near-infrared electrochromism,ion sensing,and mimicking flip-flop and flip-flap-flop logic gates.The oxidative electropolymerization of diruthenium complexes with two distal triarylamine units affords electropolymers with an alternating diruthenium and tetraphenylbenzidine structural unit.The applications of the resulting films in multistate near-infrared electrochromism and resistive memory are discussed.
文摘A new anionic dinuclear ruthenium complex bearing 1, 2-his(diphenylphosphinomethyl)benzene (BDPX) [NH2Et2][{RuCl (BDPX)}2(μ-Cl)3] (1) was synthesized and its structure was determined by an X-ray crystallo-graphic analysis. This result indicated that complex 1 consisted of an anion dinuclear BDPX-Ru and a cationic di-ethylammonium. The crystal belonged to monoclinic system, C2/c space group with a=3.3552(7) nm, b= 1.8448(4) nm, c=2.4265(5) nm, β= 101.89(3)° and Z=8. The catalytic hydrogenation activities and selectivities of complex 1 for cinnamaldehyde were investigated.
文摘Six bis-tridentate and two tris-bidentate cyclometalated ruthenium complexes with a 1,2,3-triazole-containing ligand have been prepared and characterized. Single-crystal X-ray analyses of complexes [(MeOptpy)Ru(Budtab)]-(PF6) and [(Mebip)Ru(Budtab)](PF6) are presented, where MeOptpy is 4′-p-methoxyphenyl-2,2′:6′,2"-terpyridine, Budtab is the 2-deprotonated form of 1,3-di(N-n-butyl-l,2,3-triazol-4-yl)benzene, and Mebip is bis(N-methyl-ben-zimidazolyl)pyridine. The electronic properties of these complexes are probed by spectroscopic and electrochemical analyses. Time-dependent density functional theory calculations have been performed to assist the assignment of the absorption spectra.
基金Supported by the National Natural Science Foundation of China(No.20872108)
文摘The reaction of a ruthenium carbide complex RuCl2(C:)(PCy3)2 with [H(Et2O)x]+[BF4]- at a molar ratio of 1:2 produced a two-core ruthenium carbene complex, {[RuCl(=CHPCy3)(PCy3)]2(μ-Cl)3}+·[BF4]-, in the form of a yellow-green crystalline solid in a yield of 94%. This two-core ruthenium complex is a selective catalyst for ring closing metathesis of unsubstituted terminal dienes. More importantly, no isomerized byproduct was observed for N-substrates when the two-core ruthenium complex was used as the catalyst at an elevated temperature(137 °C), indicating that the complex is a chemo-selective catalyst for ring closing metathesis reactions.
基金This work was supported by the National Natural Science Foundation of China No. 20074036.
文摘Ferrocene-terminated trans-Ru(dppm)2 (dppm=Ph2PCH2PPh2)-containing molecular wires with alligator clips were prepared. They are suitable for self-assembly on gold electrode to investigate the influence of metal incorporation on the electron transportation property of the molecular wires.
基金This work was supported by the Natural Sciences and Engineering Research Council of Canada References.
文摘A near infrared (NIR) electrochromic attenu-ator based on a dinuclear ruthenium complex and polycrys-talline tungsten oxide was fabricated and characterized. The results show that the use of the NIR-absorbing ruthenium complex as a counter electrode material can improve the device performance. By replacing the visible electrochromic ferrocene with the NIR-absorbing ruthenium complex, the optical attenuation at 1550 nm was enhanced from 19.1 to 30.0 dB and color efficiency also increased from 29.2 to 121.2 cm2/C.
基金This work was supported by NNSFC and NSF of Fujian Province
文摘The reaction between [Ru3(3-O)(-CH3CO2)6(py)2(MeOH)](PF6) (py = pyri- dine) and diphenyl-2-pyridyl-phosphine (PPh2py) gave the triruthenium cluster complex [RuIII3(3-O)(-CH3CO2)6(py)2(PPh2py)](PF6)CH2Cl2 (C40H44Cl2F6N34O13P2Ru3) which was characterized by elemental analysis, IR, UV-Vis and 31P NMR spectroscopy, and X-ray single- crystal diffraction. The structure is of monoclinic, space group P21/n with a = 16.3896(1), b = 16.8773(2), c = 19.1438(2) ? b = 95.888(1), V = 5267.47(9) ?, Mr = 1324.83, Dc = 1.671 g/cm3, F(000) = 2636, m = 1.092 mm-1 and Z = 4. The final refinement gave R = 0.0508 and wR = 0.1111 for 6987 observed reflections (I > 2s(I)). Three Ru(III) atoms bridged by m3-oxo donor form an approximately isosceles triangle. The complex shows three quasireversible one- electron processes at E1/2 = 1.22 +0.03 and 1.20 V vs. Ag/AgCl.
基金the National Natural Science Foundation of China(Nos.20343005,20473107,20673130,and 20773147)the Hong Kong PolyU Joint Supervision Scheme(A-PH78) for financial support.
文摘A series of chiral secondary alcohols were easily prepared by means of asymmetric hydrogenation of prochiral aromatic ketones using a new((Rax)-BuP)/(R,R)-DPEN-Ru(Ⅱ) complex catalyst system.The hydrogenation of 2-methylacetophenone in n-butanol (t-BuOK/Ru =45.6/1,S/C = 500,20 atm.of H2,20℃,48 h) afforded(S)-1-(2'-methylphenyl)ethanol in 92%ee and〉99% conversion.