Porous organic polymers(POPs)containing catalytically active sites are of paramount importance for heterogeneous catalysis.However,the catalytically active sites of reported POPs are mostly limited to mononuclear meta...Porous organic polymers(POPs)containing catalytically active sites are of paramount importance for heterogeneous catalysis.However,the catalytically active sites of reported POPs are mostly limited to mononuclear metal species.Herein,we report the reaction between catechol-containing POPs(Cat-POPs)and[CuIMes]n to afford the corresponding Cu^(I)_(2)-CatPOPs with a putative vicinal binuclear(catecholate)Cu^(I)_(2)moiety.The resulting Cu^(I)_(2)-CatPOPs exhibit high Brunauer–Emmett–Teller surface areas,good stability,and excellent catalytic activity toward the aerobic oxidation of a broad range of primary and secondary alcohols under mild conditions,with either 2,2,6,6-tetramethylpiperidinyl-N-oxyl or 9-azabicyclo[3.3.0]nonane-N-oxyl as the cocatalyst.As green aerobic oxidation catalysts,the Cu^(I)_(2)-CatPOPs are much more active than the correspondingmononuclear CuIICatPOPs,where each catecholate moiety only supports one CuII center;CuI-ConPOPs,where the binding sites for CuI is a nonvicinal 1,4-dihydroxybenzene moiety;and the homogeneous analogue(3,6-di-tert-butyl catecholate)Cu^(I)_(2).These results are consistent with a proposed vicinal binuclear Cu^(I)_(2)structure that can efficiently activate molecular oxygen for the aerobic oxidation of alcohols,mechanistically similar to that observed in dicopper-containing oxygenases.Our results demonstrate the facile preparation of POPs with binuclear catalytically active sites that function as green heterogeneous catalysts for efficient oxidation of alcohols.展开更多
Two new Cu（Ⅰ） complexes [CuCl（3-PyOH）（PPh_3）_2]（1） and [Cu_2（μ-Cl）_2（4-Stpy）（Ph_3P）_3]（2）（PyOH = hydroxypyridine; stpy = styrylpyridine） with triphenylphosphine and pyridine derivatives have been s...Two new Cu（Ⅰ） complexes [CuCl（3-PyOH）（PPh_3）_2]（1） and [Cu_2（μ-Cl）_2（4-Stpy）（Ph_3P）_3]（2）（PyOH = hydroxypyridine; stpy = styrylpyridine） with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2_1/c with a = 9.8945（7）, b = 37.266（2）, c = 10.9461（7） A, β = 116.0750（10）°, V = 3625.3（4） A^3, Z = 4, D_c = 1.350 Mg/cm^（-3）, μ = 0.801 mm^（-1）, F（000） = 1528, the final R = 0.0320 and w R = 0.0729 for 18568 observed reflections（I 〉 2σ（I））, R（all data） = 0.0413, wR（all data） = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P2_1/c with a = 11.290（3）, b = 20.388（5）, c = 24.092（6） A, β = 102.028（4）°, V = 5424（2） A^3, Z = 4, D_c = 1.428 Mg/cm^（-3）, μ = 1.016 mm^（-1）, F（000） = 2408, the final R = 0.0568 and w R = 0.1486 for 27644 observed reflections（I 〉 2σ（I））, R（all data） = 0.0716, wR（all data） = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu（I） complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.展开更多
The hydrothermal reactions of CuI, KI and bidentate amines [ 1,10 phenanthroline (phen) or ethylenediamine (en)] gave the three copper(I) halide compounds, Cu3I3(phen)2 (1), CuI(phen)2 (2) and 2 (3), which were stru...The hydrothermal reactions of CuI, KI and bidentate amines [ 1,10 phenanthroline (phen) or ethylenediamine (en)] gave the three copper(I) halide compounds, Cu3I3(phen)2 (1), CuI(phen)2 (2) and 2 (3), which were structurally characterized via singlecrystal Xray diffraction studies. Hydrogen bonds and ππ interactions are the most remarkable structural features of the title compounds. All can be described as higherdimensional supramolecular compounds connected via these secondary bondings. Moreover, the title compounds were characterized by elemental analyses, IR spectra and TGA analyses. The thirdorder nonlinear optical properties of the title compounds were also investigated and all exhibit nicer nonlinear absorption and selffocusing performance.Keywords copper(I) halide, hydrothermal synthesis, the thirdorder nonlinear optical property, supramolecular structure展开更多
Two new copper（I） halide complexes bearing 2-（2-benzimidazolyl）-6-methylpyridine （Hbmp） and PPh3 ligands, Cu（Hbmp）（PPh3）X （X = Br （1）; I （2））, have been synthesized and characterized. Single-crystal X-...Two new copper（I） halide complexes bearing 2-（2-benzimidazolyl）-6-methylpyridine （Hbmp） and PPh3 ligands, Cu（Hbmp）（PPh3）X （X = Br （1）; I （2））, have been synthesized and characterized. Single-crystal X-ray structure analysis reveals that the halide ligand has a significant impact on the Cu-Npyridyl bond lengths. Complexes 1 and 2 show the solid-state emissions at ambient temperature, varying with the halide bound to the { Cu（Hbmp）（PPh3） } motif, which are perhaps best attributed to the metal-to-ligand charge-transfer （Cu（I） → Hbmp） transition mixed with some ligand-to-ligand charge-transfer （X and PPh3 → Hbmp） character.展开更多
Self-assembly between Pt(phen)(edt) (phen=phenanthroline, edt=1,2-ethanedithiolate) and Cu(PPh3)2(MeCN)2(ClO4) (PPh3=triphenylphosphine) gave rise to formation of heterohexanuclear complex Pt4Cu2(edt)4(PPh3)6(ClO4)2(4...Self-assembly between Pt(phen)(edt) (phen=phenanthroline, edt=1,2-ethanedithiolate) and Cu(PPh3)2(MeCN)2(ClO4) (PPh3=triphenylphosphine) gave rise to formation of heterohexanuclear complex Pt4Cu2(edt)4(PPh3)6(ClO4)2(4H2O) (1). The complex was characterized by elemental analyses, ES-MS, UV-Vis, IR, 31P NMR spectroscopy and X-ray crystallography. The molecule consists of two Pt2Cu(edt)2(PPh3)3 units which has a centrosymmmetric inversion to give a cyclic heterohexanuclear skeleton. The PtⅡ and CuⅠ center adopt square-planar and trigonal coordination modes, respectively. The compound shows intense emission at 632 nm in the solid state and at 678 nm in frozen dichloromethane glass at 77 K.展开更多
A new candidate [Cu（PPh3）2Him]Br （1, PPh3 =triphenylphosphine, Him= 1-H-imidazole） for nonlinear optical （NLO） materials has been synthesized and characterized crystallographically. The third-order NLO optical p...A new candidate [Cu（PPh3）2Him]Br （1, PPh3 =triphenylphosphine, Him= 1-H-imidazole） for nonlinear optical （NLO） materials has been synthesized and characterized crystallographically. The third-order NLO optical properties were measured by the Z-scan technique with an 8 ns pulsed laser at 532 nm. Compound 1 exhibits strong NLO absorptive abilities [a2=（61±5）×10^-12] and effective self-focusing performance [n2=（15±3）×10^-18 m^2·W^-1] in 1.01×10^-4 molodm 3 DMF solution. The compound also exhibits luminescence in DMF solution at room temperature and shows narrow emission with maximum at 382 nm. The electronic structure and photoluminescent process were investigated by means of TD-DFT calculations. The results suggest that the contribution to the frontier orbitals from the Cu-Br σ bond plays a crucial role in its linear optical properties, and the origin of luminescence is attrib- utable to the π＊ → n transitions.展开更多
The title compound Cu 2Cl 2phen (phen=1,10 phenanthroline, C 12 H 8N 2) 1 was synthesized from CuCl 2·2H 2O, CuCl and phen by hydrothermal method and its structure was determined by single crystal X r...The title compound Cu 2Cl 2phen (phen=1,10 phenanthroline, C 12 H 8N 2) 1 was synthesized from CuCl 2·2H 2O, CuCl and phen by hydrothermal method and its structure was determined by single crystal X ray analysis. With phen, CuCl forms one dimensional chains, which comprise two zigzag chains based on fused Cu X units and connected via covalent bonds. The compound contains two crystallographically unique monovalent copper ions, Cu(1) and Cu(2). The Cu(1) atom in the tetrahedral site, is coordinated to two bridging Cl - and two N atoms in phen. The Cu(2) atom with a slightly distorted triangular planar geometry, is coordinated to three Cl -. The compound 1 was crystallized in monoclinic, space group P 2 1/ n with a = 0.37338(4) , b =1.9510(2), c =1.68008(19) nm, β =95.605(3)°, R =0.0458, and was characterized by elemental analysis, IR spectrum and TGA analysis.展开更多
The solvothermal reaction of CuI with 5-amino-2-benzimidazolethiol in acetonitrile condition affords complex [Cuz（5-amino-2-benzimidazolethiol）2]2 which has been characterized by elemental analysis, infrared spectru...The solvothermal reaction of CuI with 5-amino-2-benzimidazolethiol in acetonitrile condition affords complex [Cuz（5-amino-2-benzimidazolethiol）2]2 which has been characterized by elemental analysis, infrared spectrum and single-crystal X-ray diffraction analysis. Crystal data for C28H24N12S4Cu4： monoclinic, space group C2/c with a = 15.970（5）, b = 12.365（4）, c = 16.293（5） A, fl = 91.977（6）°, V = 3215.5（18）, Z = 4, Mr= 910.99, Dc= 1.882 g/cm3 , F（000） = 1824, p = 2.913 mm-1, λ（MoKa） = 0.71073A, T= 293（2） K, the final R = 0.0527 and wR = 0.1342. X-ray diffraction analysis revealed that the title complex exhibits a l D channel constructed from tetranuclear-copper（I） motifs connected by hydrogen bonds and shows strong photoluminescence in the solid state at room temperature.展开更多
A novel and effective protocol has been developed for the Ullmann-type C--N coupling reaction catalyzed by calix[4]arene supported amino acid ionic liquid and copper（I） iodide in water under microwave irradiation co...A novel and effective protocol has been developed for the Ullmann-type C--N coupling reaction catalyzed by calix[4]arene supported amino acid ionic liquid and copper（I） iodide in water under microwave irradiation condition The protocol uses ealix[4]arene supported amino acid ionic liquid as double function of the ligand and phase-transfer catalyst, and shows good tolerance in good to excellent yields.展开更多
A new and efficient cascade synthesis of indazolo[2,1-a]indazole-6,12-diones has been developed. This protocol includes an intermolecular N-acylation followed by a copper-catalyzed intramolecular C--N coupling reactio...A new and efficient cascade synthesis of indazolo[2,1-a]indazole-6,12-diones has been developed. This protocol includes an intermolecular N-acylation followed by a copper-catalyzed intramolecular C--N coupling reaction. The methodology is applied to a wide range of 2-bromo and 2-chloro benzoyl chlorides to yield the indazolo- [2,1-a]indazole-6,l 2-diones in good to excellent yields with high regioselectivities.展开更多
A new and efficient cascade synthesis of polycyclic fused imidazo[2,1-b][1,3]thiazinones has been developed. This protocol includes an intermolecular N-acylation followed by a copper-catalyzed intramolecular C--S coup...A new and efficient cascade synthesis of polycyclic fused imidazo[2,1-b][1,3]thiazinones has been developed. This protocol includes an intermolecular N-acylation followed by a copper-catalyzed intramolecular C--S coupling reaction. The methodology is applied to a wide range of 2-iodo, 2-bromo, and 2-chloro benzoyl chlorides to yield the polycyclic fused imidazo[2,1-b][ 1,3]thiazinones in good to excellent yields.展开更多
Density functional theory（DFT） calculations unambiguously verify that there is little or no direct metalmetal bonding in the dinuclear copper（I） benzamidinate complex [Cu2（LRW）2]（2）{LRR=[PhC（NR）（NR＇）]-（R...Density functional theory（DFT） calculations unambiguously verify that there is little or no direct metalmetal bonding in the dinuclear copper（I） benzamidinate complex [Cu2（LRW）2]（2）{LRR=[PhC（NR）（NR＇）]-（R= 2,6-iPr2C6H3, R＇=SiMe3）} with a short Cu-Cu distance[0.24454（4） nm].展开更多
A new Cu（I）-dicyanamide with formula [Cu2（L）（dca）2]n （dca = dicyanamide anion, L = 1,4-bis（3-furanyl）-2,3-diaza-1,3-butadiene） has been synthesized and structurally characterized. The complex crystallizes in...A new Cu（I）-dicyanamide with formula [Cu2（L）（dca）2]n （dca = dicyanamide anion, L = 1,4-bis（3-furanyl）-2,3-diaza-1,3-butadiene） has been synthesized and structurally characterized. The complex crystallizes in the monoclinic system, space group P21/n with a = 9.271（2）, b = 7.7355（16）, c = 11.967（3）A,β = 102.693（3）°, V= 837.3（3）A^3, Z = 4, Mr = 223.68, Dc = 1.775 g/cm^3,μ（MoKa） = 2.567 mm^-1, F（000） = 444, R = 0.0782 and wR = 0.2582 for 951 observed reflections （I 〉 2σ（I））. Single-crystal X-ray analysis reveals that the copper atom is three-coordinated by two nitrogen atoms from two dicyanamide anions and another one from the ligand, and each copper atom is connected by two [N（CN）2] anions to form an infinite double-stranded bridge fashion leading to 1D ladder-like motifs.展开更多
基金support from the National Natural Science Foundation of China(no.52103328)the Guangdong Basic and Applied Basic Research Foundation(no.2020A1515110575)the Science and Technology Program of Guangzhou(no.202102020422),and the Sun Yat-sen University Start-up Funding.S.T.N.is grateful for the financial support from DTRA(no.HDTRA1-14-1-0014),the U.S.Department of Energy(DOE)(no.DE FG02-03-ER154757 to the Institute of Catalysis for Energy Processes(ICEP)at Northwestern University).Work at Argonne National Laboratory was supported by the U.S.Department of Energy(DOE),Office of Basic Energy Sciences,Division of Chemical Sciences,Geosciences,and Biosciences,under Contract DEAC02-06CH11357.Experimental facilities at the Integrated Molecular Structure Education and Research Center(IMSERC)and the Northwestern University Atomic and Nanoscale Characterization Experimental Center(EPIC,Keck-II)at Northwestern University(NU)were purchased with grants from NSFNSEC,NSF-MRSEC,the Keck Foundation,the state of Illinois,and Northwestern University.ICP-OES analyses were carried out at the Northwestern University Quantitative Bio-element Imaging Center.
文摘Porous organic polymers(POPs)containing catalytically active sites are of paramount importance for heterogeneous catalysis.However,the catalytically active sites of reported POPs are mostly limited to mononuclear metal species.Herein,we report the reaction between catechol-containing POPs(Cat-POPs)and[CuIMes]n to afford the corresponding Cu^(I)_(2)-CatPOPs with a putative vicinal binuclear(catecholate)Cu^(I)_(2)moiety.The resulting Cu^(I)_(2)-CatPOPs exhibit high Brunauer–Emmett–Teller surface areas,good stability,and excellent catalytic activity toward the aerobic oxidation of a broad range of primary and secondary alcohols under mild conditions,with either 2,2,6,6-tetramethylpiperidinyl-N-oxyl or 9-azabicyclo[3.3.0]nonane-N-oxyl as the cocatalyst.As green aerobic oxidation catalysts,the Cu^(I)_(2)-CatPOPs are much more active than the correspondingmononuclear CuIICatPOPs,where each catecholate moiety only supports one CuII center;CuI-ConPOPs,where the binding sites for CuI is a nonvicinal 1,4-dihydroxybenzene moiety;and the homogeneous analogue(3,6-di-tert-butyl catecholate)Cu^(I)_(2).These results are consistent with a proposed vicinal binuclear Cu^(I)_(2)structure that can efficiently activate molecular oxygen for the aerobic oxidation of alcohols,mechanistically similar to that observed in dicopper-containing oxygenases.Our results demonstrate the facile preparation of POPs with binuclear catalytically active sites that function as green heterogeneous catalysts for efficient oxidation of alcohols.
基金Supported by the National Natural Science Foundation of China(NSFC 21102102)
文摘Two new Cu（Ⅰ） complexes [CuCl（3-PyOH）（PPh_3）_2]（1） and [Cu_2（μ-Cl）_2（4-Stpy）（Ph_3P）_3]（2）（PyOH = hydroxypyridine; stpy = styrylpyridine） with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2_1/c with a = 9.8945（7）, b = 37.266（2）, c = 10.9461（7） A, β = 116.0750（10）°, V = 3625.3（4） A^3, Z = 4, D_c = 1.350 Mg/cm^（-3）, μ = 0.801 mm^（-1）, F（000） = 1528, the final R = 0.0320 and w R = 0.0729 for 18568 observed reflections（I 〉 2σ（I））, R（all data） = 0.0413, wR（all data） = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P2_1/c with a = 11.290（3）, b = 20.388（5）, c = 24.092（6） A, β = 102.028（4）°, V = 5424（2） A^3, Z = 4, D_c = 1.428 Mg/cm^（-3）, μ = 1.016 mm^（-1）, F（000） = 2408, the final R = 0.0568 and w R = 0.1486 for 27644 observed reflections（I 〉 2σ（I））, R（all data） = 0.0716, wR（all data） = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu（I） complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.
基金theNationalNaturalScienceFoundationofChina (No .2 97330 90 )theDoctoralProgramofHigherEducation(No.19990 18310 )
文摘The hydrothermal reactions of CuI, KI and bidentate amines [ 1,10 phenanthroline (phen) or ethylenediamine (en)] gave the three copper(I) halide compounds, Cu3I3(phen)2 (1), CuI(phen)2 (2) and 2 (3), which were structurally characterized via singlecrystal Xray diffraction studies. Hydrogen bonds and ππ interactions are the most remarkable structural features of the title compounds. All can be described as higherdimensional supramolecular compounds connected via these secondary bondings. Moreover, the title compounds were characterized by elemental analyses, IR spectra and TGA analyses. The thirdorder nonlinear optical properties of the title compounds were also investigated and all exhibit nicer nonlinear absorption and selffocusing performance.Keywords copper(I) halide, hydrothermal synthesis, the thirdorder nonlinear optical property, supramolecular structure
基金support from the NNSFC(Nos21163009 and 21001057)the Key Project of Chinese Ministry of Education(No211088)+2 种基金the Advanced Program for the Retuned Overseas Chinese Scholars of the MOHRSS(No 474[2011])the Training Program for Jiangxi Provincial Young Scientiststhe Foundation of State Key Laboratory of Structural Chemistry(No20110015)
文摘Two new copper（I） halide complexes bearing 2-（2-benzimidazolyl）-6-methylpyridine （Hbmp） and PPh3 ligands, Cu（Hbmp）（PPh3）X （X = Br （1）; I （2））, have been synthesized and characterized. Single-crystal X-ray structure analysis reveals that the halide ligand has a significant impact on the Cu-Npyridyl bond lengths. Complexes 1 and 2 show the solid-state emissions at ambient temperature, varying with the halide bound to the { Cu（Hbmp）（PPh3） } motif, which are perhaps best attributed to the metal-to-ligand charge-transfer （Cu（I） → Hbmp） transition mixed with some ligand-to-ligand charge-transfer （X and PPh3 → Hbmp） character.
文摘Self-assembly between Pt(phen)(edt) (phen=phenanthroline, edt=1,2-ethanedithiolate) and Cu(PPh3)2(MeCN)2(ClO4) (PPh3=triphenylphosphine) gave rise to formation of heterohexanuclear complex Pt4Cu2(edt)4(PPh3)6(ClO4)2(4H2O) (1). The complex was characterized by elemental analyses, ES-MS, UV-Vis, IR, 31P NMR spectroscopy and X-ray crystallography. The molecule consists of two Pt2Cu(edt)2(PPh3)3 units which has a centrosymmmetric inversion to give a cyclic heterohexanuclear skeleton. The PtⅡ and CuⅠ center adopt square-planar and trigonal coordination modes, respectively. The compound shows intense emission at 632 nm in the solid state and at 678 nm in frozen dichloromethane glass at 77 K.
基金Acknowledgement This work was supported by the NSF of China （No. 20871072）, the NSF of Shandong Province （No. 2009ZRA02071）, the Scientific Development Plan of University in Shandong Province （No. J09LB53）, and the Doctoral Science Foundation of QUST.
文摘A new candidate [Cu（PPh3）2Him]Br （1, PPh3 =triphenylphosphine, Him= 1-H-imidazole） for nonlinear optical （NLO） materials has been synthesized and characterized crystallographically. The third-order NLO optical properties were measured by the Z-scan technique with an 8 ns pulsed laser at 532 nm. Compound 1 exhibits strong NLO absorptive abilities [a2=（61±5）×10^-12] and effective self-focusing performance [n2=（15±3）×10^-18 m^2·W^-1] in 1.01×10^-4 molodm 3 DMF solution. The compound also exhibits luminescence in DMF solution at room temperature and shows narrow emission with maximum at 382 nm. The electronic structure and photoluminescent process were investigated by means of TD-DFT calculations. The results suggest that the contribution to the frontier orbitals from the Cu-Br σ bond plays a crucial role in its linear optical properties, and the origin of luminescence is attrib- utable to the π＊ → n transitions.
文摘The title compound Cu 2Cl 2phen (phen=1,10 phenanthroline, C 12 H 8N 2) 1 was synthesized from CuCl 2·2H 2O, CuCl and phen by hydrothermal method and its structure was determined by single crystal X ray analysis. With phen, CuCl forms one dimensional chains, which comprise two zigzag chains based on fused Cu X units and connected via covalent bonds. The compound contains two crystallographically unique monovalent copper ions, Cu(1) and Cu(2). The Cu(1) atom in the tetrahedral site, is coordinated to two bridging Cl - and two N atoms in phen. The Cu(2) atom with a slightly distorted triangular planar geometry, is coordinated to three Cl -. The compound 1 was crystallized in monoclinic, space group P 2 1/ n with a = 0.37338(4) , b =1.9510(2), c =1.68008(19) nm, β =95.605(3)°, R =0.0458, and was characterized by elemental analysis, IR spectrum and TGA analysis.
基金Supported by the 973 key program of the MOST(2010CB933501,2012CB821705)the Chinese Academy of Sciences(KJCX2-YW-319,KJCX2-EW-H01)+1 种基金the National Natural Science Foundation of Chinathe Natural Science Foundation of Fujian Province(2007HZ0001-1,2009HZ0004-1,2009HZ0005-1,2009HZ0006-1,2006L2005)
文摘The solvothermal reaction of CuI with 5-amino-2-benzimidazolethiol in acetonitrile condition affords complex [Cuz（5-amino-2-benzimidazolethiol）2]2 which has been characterized by elemental analysis, infrared spectrum and single-crystal X-ray diffraction analysis. Crystal data for C28H24N12S4Cu4： monoclinic, space group C2/c with a = 15.970（5）, b = 12.365（4）, c = 16.293（5） A, fl = 91.977（6）°, V = 3215.5（18）, Z = 4, Mr= 910.99, Dc= 1.882 g/cm3 , F（000） = 1824, p = 2.913 mm-1, λ（MoKa） = 0.71073A, T= 293（2） K, the final R = 0.0527 and wR = 0.1342. X-ray diffraction analysis revealed that the title complex exhibits a l D channel constructed from tetranuclear-copper（I） motifs connected by hydrogen bonds and shows strong photoluminescence in the solid state at room temperature.
基金We gratefully acknowledge financial support from the National Natural Science Foundation of China （No. 21176222）.
文摘A novel and effective protocol has been developed for the Ullmann-type C--N coupling reaction catalyzed by calix[4]arene supported amino acid ionic liquid and copper（I） iodide in water under microwave irradiation condition The protocol uses ealix[4]arene supported amino acid ionic liquid as double function of the ligand and phase-transfer catalyst, and shows good tolerance in good to excellent yields.
基金Project supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions, the National Natural Science Foundation of China （Nos. 21072168, 21102009） and Natural Science Foundation of Jiangsu Province （No. BK2011230）.
文摘A new and efficient cascade synthesis of indazolo[2,1-a]indazole-6,12-diones has been developed. This protocol includes an intermolecular N-acylation followed by a copper-catalyzed intramolecular C--N coupling reaction. The methodology is applied to a wide range of 2-bromo and 2-chloro benzoyl chlorides to yield the indazolo- [2,1-a]indazole-6,l 2-diones in good to excellent yields with high regioselectivities.
基金Project supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions, the National Natural Science Foundation of China （Nos. 21072168, 21102009） and Natural Science Foundation of Jiangsu Province （No. B K2011230）.
文摘A new and efficient cascade synthesis of polycyclic fused imidazo[2,1-b][1,3]thiazinones has been developed. This protocol includes an intermolecular N-acylation followed by a copper-catalyzed intramolecular C--S coupling reaction. The methodology is applied to a wide range of 2-iodo, 2-bromo, and 2-chloro benzoyl chlorides to yield the polycyclic fused imidazo[2,1-b][ 1,3]thiazinones in good to excellent yields.
基金Supported by the National Natural Science Foundation of China（No.21201006）, the Special Research Fund for the Doctoral Program of Higher Education of China（No.26920123415120002） and the Fund of the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry of China（No.2012-27）.Acknowledgements We thank Prof ZHANG Hongjie（Changchun Institute of Applied Chemistry, Chinese Academy of Sciences） for his helpful suggestions.
文摘Density functional theory（DFT） calculations unambiguously verify that there is little or no direct metalmetal bonding in the dinuclear copper（I） benzamidinate complex [Cu2（LRW）2]（2）{LRR=[PhC（NR）（NR＇）]-（R= 2,6-iPr2C6H3, R＇=SiMe3）} with a short Cu-Cu distance[0.24454（4） nm].
基金the NNSFC(Nos.20561004and20761005)the Key Project of Chinese Ministry of Education(No.205147)+1 种基金the Specialized Research Fund for the Doctoral Program of Higher Education(No.20060673015)NSF of Yunnan Province(No.2003RC13)
文摘A new Cu（I）-dicyanamide with formula [Cu2（L）（dca）2]n （dca = dicyanamide anion, L = 1,4-bis（3-furanyl）-2,3-diaza-1,3-butadiene） has been synthesized and structurally characterized. The complex crystallizes in the monoclinic system, space group P21/n with a = 9.271（2）, b = 7.7355（16）, c = 11.967（3）A,β = 102.693（3）°, V= 837.3（3）A^3, Z = 4, Mr = 223.68, Dc = 1.775 g/cm^3,μ（MoKa） = 2.567 mm^-1, F（000） = 444, R = 0.0782 and wR = 0.2582 for 951 observed reflections （I 〉 2σ（I））. Single-crystal X-ray analysis reveals that the copper atom is three-coordinated by two nitrogen atoms from two dicyanamide anions and another one from the ligand, and each copper atom is connected by two [N（CN）2] anions to form an infinite double-stranded bridge fashion leading to 1D ladder-like motifs.
