Two new copper complexes based on pyrazole-3-carboxylic acid （H2pca） ligand, Cu（Hpca）2（H2O）2？2H2O （1） and Cu2（pca）2（H2O）4 （2） have been synthesized and fully characterized by single-crystal X-ray diffra...Two new copper complexes based on pyrazole-3-carboxylic acid （H2pca） ligand, Cu（Hpca）2（H2O）2？2H2O （1） and Cu2（pca）2（H2O）4 （2） have been synthesized and fully characterized by single-crystal X-ray diffraction （SXRD）, infrared spectroscopy （IR）, thermal gravity analysis （TGA）, powder X-ray diffraction （PXRD） and elemental analyses. Complex 1 is mononuclear while complex 2 shows a dinuclear structure. Complex 1 crystallizes in the monoclinic system, space group P21/c with Z = 2, a = 6.5591（5）, b = 21.696（2）, c = 4.9486（2） ？, V = 680.94（9） ？3, F（000） = 366, Dc = 1.745 g/cm3, μ = 1.650 mm-1, the final R = 0.0340 and wR = 0.0792. Complex 2 crystallizes in the monoclinic system, space group P21/n with Z = 2, a = 5.1935（4）, b = 9.6052（7）, c = 12.7347（9） ？, V = 634.44（8） ？3, F（000） = 420, Dc = 2.195 g/cm3, μ = 3.404 mm-1, the final R = 0.0305 and wR = 0.0653. The three-dimensional frameworks of two complexes are formed by the O？H？？？O and N？H？？？O hydrogen bonding interactions. Notably, two copper complexes are further used as catalysts in the oxidation of alkylbenzenes using t-butylhydroperoxide （TBHP） as the oxidant and they exhibit excellent catalytic performance （Conv. up to 98.9%, Sele. up to 98.7%）.展开更多
The luminescent mechanism and properties of a triangular Cu（I） complex, （CuPz）3. have been studied by CIS method. The ground and lowest triplet excitation state geometries were optimized at MP2/SBKJC and CIS/SBKJC...The luminescent mechanism and properties of a triangular Cu（I） complex, （CuPz）3. have been studied by CIS method. The ground and lowest triplet excitation state geometries were optimized at MP2/SBKJC and CIS/SBKJC levels, respectively. A remarkable geometry distortion of the lowest triplet state was found and believed to cause the emission spectra to red shift.展开更多
Aqua[(6-carboxyl-2-pyridilamide)histaminato]copper(II)1 was synthesized for study of MPV(molecular parity violation).Crystal structure of 1 was defined by X-ray crystallographic analysis to give racemic structure cons...Aqua[(6-carboxyl-2-pyridilamide)histaminato]copper(II)1 was synthesized for study of MPV(molecular parity violation).Crystal structure of 1 was defined by X-ray crystallographic analysis to give racemic structure consisting of planar-R(pR)and planar-S(pS)enantiomers.Each enantiomer was square pyramidal five coordinated copper complex with the fifth apical ligand of H2O molecule.Specific rotation of the time development analysis of 1 gave mutarotation phenomenon from pR enantiomer priority side([α ]D:+2,450°)to pS enantiomer priority state([α ]D:-1,240°)in MeOH.Chiral irradiation energy of the detector from outside gave dynamic equilibrium between enantiomers,resulted to give pS enantiomer priority state with dissipative process.MPV of 1 was followed that the parity inversion of chiral restraint dz2 orbital brought about inversion of chiral coordination sphere along z-axis for alternative replacement of the fifth apical ligand to solvent molecule on copper atom.SMPV(spontaneous molecular parity violation)of 1 was observed vice versa on transfiguration of specific rotation from the last pS enantiomer priority state([α ]D:-1,240°)to pR enantiomer priority side([α ]D:+2,450°)without chiral irradiation of optical detector,until reset analysis of the same sample.Therefore,the pR enantiomer priority state had existed in the lowest free energy of the ground state as visually unobservable SMPV state of 1 in the solvent.展开更多
HN(CH_(2)CH_(2)PR_(2))2-ligated copper borohydride complexes,(^(R)PN^(H)P)Cu(BH4)(R=iPr,Cy,tBu),which can be prepared from(^(R)PN^(H)P)CuBr and NaBH4,are capable of catalyzing the hydrogenation of aldehydes in an alco...HN(CH_(2)CH_(2)PR_(2))2-ligated copper borohydride complexes,(^(R)PN^(H)P)Cu(BH4)(R=iPr,Cy,tBu),which can be prepared from(^(R)PN^(H)P)CuBr and NaBH4,are capable of catalyzing the hydrogenation of aldehydes in an alcoholic solvent.More active hydrogenation catalysts are(^(R)PN^(H)P)CuBr mixed with KO^(t)Bu,allowing various aldehydes and ketones to be efficiently reduced to alcohols except those bearing a nitro,N-unprotected pyrrole,pyridine,or an ester group,or those prone to aldol condensation(e.g.,1-heptanal).Modifying the catalyst structure by replacing the NH group in(^(iPr)PN^(H)P)CuBr with an NMe group results in an inferior catalyst but preserves some catalytic activity.The hexanuclear copper hydride cluster,(^(iPr)PN^(H)P)_(3)Cu_(6)H_(6),is also competent in catalyzing the hydrogenation of aldehydes such as benzaldehyde and N-methyl-2-pyrrolecarboxaldehyde,albeit accompanied by decomposition pathways.The catalytic performance can be enhanced through the addition of a strong base or^(iPr)PN^(H)P.The three catalytic systems likely share the same catalytically active species,which is proposed to be a mononuclear copper hydride(^(R)PN^(H)P)CuH with the NH group bound to copper.展开更多
Photovoltaics with dye-sensitized solar cells have been recognized as being promising for the utilization of sunlight to produce electricity and‘solar chemicals’.One of the remaining unsolved challenges is the devel...Photovoltaics with dye-sensitized solar cells have been recognized as being promising for the utilization of sunlight to produce electricity and‘solar chemicals’.One of the remaining unsolved challenges is the development of an affordable,robust dye that has a panchromatic light harvesting range and efficiently provides separated charges for the desired photochemistry.The most commonly employed molecular photosensitizers include the noble metal-based ruthenium and iridium complexes,synthetically challenging porphyrin derivatives,and expensive,functionalized polypyridine compounds.Here,we describe the development of Cu(I)dyes supported by bis(arylimino)acenaphthene(Ar-BIAN)ligands,which can be synthesized in fewer than three steps from affordable,commercially available reagents.展开更多
In this study,two copper(II)salts with different configurations,2[H_(3)LCuCl_(4)][Cu_(2)Cl_(6)](1)and[H_(4)L][CuCl_(4)]_(2)Cl(2)(L=(1R,2R)-N,N’-bis(pyridin-4-ylmethyl)cyclohexane-1,2-diamine),have been synthesized an...In this study,two copper(II)salts with different configurations,2[H_(3)LCuCl_(4)][Cu_(2)Cl_(6)](1)and[H_(4)L][CuCl_(4)]_(2)Cl(2)(L=(1R,2R)-N,N’-bis(pyridin-4-ylmethyl)cyclohexane-1,2-diamine),have been synthesized and applied in the following solid–gas and solid–solid reactions.Both salts 1 and 2 gave rise to the salt([H_(4)L][Cu_(2)Cl_(8)]H_(2)O(3)upon exposure to HCl gas or grinding with equal moles of CuCl_(2)·2H_(2)O.展开更多
Thioether-containing pyridylalkylamide ligands 2-(methylsulfanyl)-N-[2-(pyridine-2-yl)methyl]acetamide(HL1)and 2-(methylsulfanyl)-N-[2-(pyridine-2-yl)ethyl]acetamide(HL2)were synthesized and fully characterized.Three ...Thioether-containing pyridylalkylamide ligands 2-(methylsulfanyl)-N-[2-(pyridine-2-yl)methyl]acetamide(HL1)and 2-(methylsulfanyl)-N-[2-(pyridine-2-yl)ethyl]acetamide(HL2)were synthesized and fully characterized.Three copper complexes{[Cu(L1)(CH3OH)](OTf)}n(1),(OTf=triflate),{[Cu(L2)(OTf)].CH3OH}n(2)and[Cu(HL2)(CH3OH)C1](3)were synthesized and characterized with X-ray diffraction methods.The single-crystal X-ray analyses indicate that complex 1 and 2 form 1D coordination polymers,while complex 3 is a mononuelear copper complex.The coordination modes of the copper ion are analyzed and the reasons are interpreted.CCDC:1421197,1;1421198,2;1421199,3.展开更多
Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron...Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.展开更多
1 Introduction Immobilization of homogeneous catalysts onto polymer supports through covalent attachment has received wide attention because these materials offer advantage features of heterogeneous catalysis to homog...1 Introduction Immobilization of homogeneous catalysts onto polymer supports through covalent attachment has received wide attention because these materials offer advantage features of heterogeneous catalysis to homogeneous systems.The polymer-supported catalysts enhance their thermal stability,selectivity,recyclability and easy separation from reaction products leading to the operationally flexible[1-2].Such behaviour prompted us to know the effect of pore structures of polymer supporters on catalytic ...展开更多
Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co（Ⅱ） acetate tetrahydrate in anhydrous ethanol and L-leucinol ...Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co（Ⅱ） acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu（Ⅱ） chloride dihydrate in anhydrous methanol. The structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Co3（C51H66N3O16）]2（OAc）, monoclinic, space group P21, a = 15.022（3）, b = 14.242（3）, c = 28.922（6） A, β = 98.944（4）°, V = 6112（2） A3, Z = 4, Dc = 1.339 g/cm^3, the final R = 0.0860 for 21906 observed reflections with I 〉 2（I）. For Ⅱ： Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a = 6.1861（13）, b = 20.838（4）, c = 28.274（6） , V = 3644.6（13） 3, Z = 4, Dc = 1.310 g/cm^3, the final R = 0.0642 for 11106 observed reflections with I 〉 2（I）. The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.展开更多
Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal s...Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.展开更多
Introduction Nucleases which catalyze the hydrolytic cleavage of the phosphodiester backbone of DNA and RN A play animportant role in the molecular genetics and genetic engineering.The development of reagents which hy...Introduction Nucleases which catalyze the hydrolytic cleavage of the phosphodiester backbone of DNA and RN A play animportant role in the molecular genetics and genetic engineering.The development of reagents which hydrolytically cleave nucleic acids under mild conditions has currently been attracting great interest in the field of artificial nucleases"",for example,the small metal complexes that promote the hydrolysis of DNA and RNA are useful not only in molecular biology and drug design but also in elucidating the role of metal ions in enzyme catalysis.展开更多
The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been s...The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1： orthorhombic, space group Pbca with a = 11.921（4）, b = 15.816（6）, c = 17.076（6） A, V= 3219.7（19） A^3, C15H17CuN3O5S, Z = 8, Mr = 414.92, De = 1.712 g/cm^3,μ（MoKα） = 1.520 mm^-1, F（000） = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I 〉 2σ（I）; and crystal data for 2： monoclinic, space group P21/c with a = 7.929（3）, b = 17.038（5）, c = 11.734（4） A, β = 98.162（6）°, V = 1569.1（9） A^3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm^3, F（000） = 820,μ（MoKα） = 1.554 mm^-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections （I 〉 2σ（I））. The molecular structure of complex 1 consists of one tetra-coordinated Cu（Ⅱ） atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper（Ⅱ） structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.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
Modified α and β bis(salicylaldoxime)copper(Ⅱ) have been obtained by recrystallization from ethyl acetate(CCDC Nos. 212157 & 212158). The X-ray analysis reveals that the two modificated forms have the same stru...Modified α and β bis(salicylaldoxime)copper(Ⅱ) have been obtained by recrystallization from ethyl acetate(CCDC Nos. 212157 & 212158). The X-ray analysis reveals that the two modificated forms have the same structure with different geometric parameters. The α form crystallizes in the P2(1)/c space group and the β form in the P1 space group. Both the crystal structures consist of centrosymmetric monomeric molecules of Cu(OC_6H_4CNOH)_2. The IR spectra are in agreement with the structural data.展开更多
A flexible double betaine 1,4-bis（pyridinil-4-carboxylato）-1,4-dimethylbenzene L has been used to generate two Cu（Ⅱ）-containing metal complexes that exhibit different polymeric structures： [Cu（H2O）2 L].2NO3 1 ...A flexible double betaine 1,4-bis（pyridinil-4-carboxylato）-1,4-dimethylbenzene L has been used to generate two Cu（Ⅱ）-containing metal complexes that exhibit different polymeric structures： [Cu（H2O）2 L].2NO3 1 and [Cu（H2O）3 L].2Cl.H2O 2. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction method. Crystal data for 1： triclinic, space group PT, a = 5.253（2）, b = 7.406（3）, c = 14.792（5） A, α = 84.195（5）, β = 80.014（5）, γ = 78.053（5）°, V= 553.2（3）A^3, Z = 1, F（000） = 293, Dc = 1.717 g/cm^3, the final R = 0.0385 and wR = 0.1079 for 1883 observed reflections （I 〉 2σ（I））; and those for 2： monoclinic, space group P21/c, a = 10.222（3）, b = 25.287（7）, c = 9.277（3）A, β = 93.572（5）°, V = 2393.2（12）A^3, Z = 4, F（000） = 1140, Dc = 1.540 g/cm^3, the final R = 0.0472 and wR = 0.0956 for 3204 observed reflections （I 〉2o（/））.展开更多
Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terp...Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.展开更多
Computational calculation was performed to investigate the mechanism of trifluoromethylation reactions of iodobenzene with well-defined N-heterocyclic carbene （NHC）-supported Cu~ trifiuor- omethyl complexes. Four pr...Computational calculation was performed to investigate the mechanism of trifluoromethylation reactions of iodobenzene with well-defined N-heterocyclic carbene （NHC）-supported Cu~ trifiuor- omethyl complexes. Four proposed reaction pathways, namely cr-bond metathesis （BM）, concerted oxidative addition-reductive elimination （OARE）, iodine atom transfer （IAT） and single-electron transfer （SET）, have been computed by density functional theory （DFT）. The result indicated that the concerted OARE mechanism is favored among the four reaction pathways, suggesting the trifluoromethylation may occur via concerted OARE mechanism involving Ar-X oxidative addition to the Cu（1） center as the rate determining step.展开更多
A couple of chiral mononuclear copper(II)-tyrosine complexes[Cu(L-Tyr)_(2)](1)and[Cu(D-Tyr)_(2)](2)[Tyr=tyrosine]have been successfully synthesized in the aqueous solution and further characterized by elemental analys...A couple of chiral mononuclear copper(II)-tyrosine complexes[Cu(L-Tyr)_(2)](1)and[Cu(D-Tyr)_(2)](2)[Tyr=tyrosine]have been successfully synthesized in the aqueous solution and further characterized by elemental analyses,IR spectra,single-crystal X-ray diffraction and circular dichroism(CD)spectroscopy.Structural analysis indicates that 1 and 2 exhibit the interesting 1-D chainlike arrangement architected from the[Cu(L-Tyr)_(2)]or[Cu(D-Tyr)_(2)]units connected by Cu-O linkages.From the view of supramolecular chemistry,neighboring[Cu(L-Tyr)_(2)]or[Cu(D-Tyr)_(2)]units are interlinked through weak hydrogen-bonding interactions constructing the 3-D supramolecular structure.Variable-temperature magnetic susceptibilities of 1 and 2 were investigated,indicating that 1 and 2 exhibit the dominant ferromagnetic behavior.Moreover,the field-dependent magnetization mea-surements suggest that 1 and 2 possess an S=1/2 ground state.展开更多
基金supported by the NNSFC(Nos.21401094 and 21501086)the Project of Shandong Province Higher Educational Science and Technology Program(No.J16LC53)the College Students'Science and Technology Innovation Fund(No.CXCY2017028 and CXCY2017037)
文摘Two new copper complexes based on pyrazole-3-carboxylic acid （H2pca） ligand, Cu（Hpca）2（H2O）2？2H2O （1） and Cu2（pca）2（H2O）4 （2） have been synthesized and fully characterized by single-crystal X-ray diffraction （SXRD）, infrared spectroscopy （IR）, thermal gravity analysis （TGA）, powder X-ray diffraction （PXRD） and elemental analyses. Complex 1 is mononuclear while complex 2 shows a dinuclear structure. Complex 1 crystallizes in the monoclinic system, space group P21/c with Z = 2, a = 6.5591（5）, b = 21.696（2）, c = 4.9486（2） ？, V = 680.94（9） ？3, F（000） = 366, Dc = 1.745 g/cm3, μ = 1.650 mm-1, the final R = 0.0340 and wR = 0.0792. Complex 2 crystallizes in the monoclinic system, space group P21/n with Z = 2, a = 5.1935（4）, b = 9.6052（7）, c = 12.7347（9） ？, V = 634.44（8） ？3, F（000） = 420, Dc = 2.195 g/cm3, μ = 3.404 mm-1, the final R = 0.0305 and wR = 0.0653. The three-dimensional frameworks of two complexes are formed by the O？H？？？O and N？H？？？O hydrogen bonding interactions. Notably, two copper complexes are further used as catalysts in the oxidation of alkylbenzenes using t-butylhydroperoxide （TBHP） as the oxidant and they exhibit excellent catalytic performance （Conv. up to 98.9%, Sele. up to 98.7%）.
基金This work was supported by the Youth Innovation Fund of Fujian Province of China (No. 2003J043), National Science Foundation of China (No. 90203017, 20573114) and 973-Plan (No. 2004CB720605)
文摘The luminescent mechanism and properties of a triangular Cu（I） complex, （CuPz）3. have been studied by CIS method. The ground and lowest triplet excitation state geometries were optimized at MP2/SBKJC and CIS/SBKJC levels, respectively. A remarkable geometry distortion of the lowest triplet state was found and believed to cause the emission spectra to red shift.
基金The author acknowledges Dr.Mikio Yamasaki and Dr.Kunihisa Sugimoto for X-ray diffraction measurements in Rigaku Corporation,and Professor Tadashi Ema in Okayama University for re-measurements of optical rotational analysis data.
文摘Aqua[(6-carboxyl-2-pyridilamide)histaminato]copper(II)1 was synthesized for study of MPV(molecular parity violation).Crystal structure of 1 was defined by X-ray crystallographic analysis to give racemic structure consisting of planar-R(pR)and planar-S(pS)enantiomers.Each enantiomer was square pyramidal five coordinated copper complex with the fifth apical ligand of H2O molecule.Specific rotation of the time development analysis of 1 gave mutarotation phenomenon from pR enantiomer priority side([α ]D:+2,450°)to pS enantiomer priority state([α ]D:-1,240°)in MeOH.Chiral irradiation energy of the detector from outside gave dynamic equilibrium between enantiomers,resulted to give pS enantiomer priority state with dissipative process.MPV of 1 was followed that the parity inversion of chiral restraint dz2 orbital brought about inversion of chiral coordination sphere along z-axis for alternative replacement of the fifth apical ligand to solvent molecule on copper atom.SMPV(spontaneous molecular parity violation)of 1 was observed vice versa on transfiguration of specific rotation from the last pS enantiomer priority state([α ]D:-1,240°)to pR enantiomer priority side([α ]D:+2,450°)without chiral irradiation of optical detector,until reset analysis of the same sample.Therefore,the pR enantiomer priority state had existed in the lowest free energy of the ground state as visually unobservable SMPV state of 1 in the solvent.
基金the NSF Chemical Catalysis Program(CHE-1464734 and CHE-1800151)the NSF MRI Program(CHE-0215950 for a Bruker APEX-II CCD diffractometer and CHE-1726092 for a Bruker Avance NEO 400 MHz NMR spectrometer)the University of Cincinnati(Doctoral Enhancement Fellowship to D.A.Ekanayake and A.Chakraborty)for support of this research.
文摘HN(CH_(2)CH_(2)PR_(2))2-ligated copper borohydride complexes,(^(R)PN^(H)P)Cu(BH4)(R=iPr,Cy,tBu),which can be prepared from(^(R)PN^(H)P)CuBr and NaBH4,are capable of catalyzing the hydrogenation of aldehydes in an alcoholic solvent.More active hydrogenation catalysts are(^(R)PN^(H)P)CuBr mixed with KO^(t)Bu,allowing various aldehydes and ketones to be efficiently reduced to alcohols except those bearing a nitro,N-unprotected pyrrole,pyridine,or an ester group,or those prone to aldol condensation(e.g.,1-heptanal).Modifying the catalyst structure by replacing the NH group in(^(iPr)PN^(H)P)CuBr with an NMe group results in an inferior catalyst but preserves some catalytic activity.The hexanuclear copper hydride cluster,(^(iPr)PN^(H)P)_(3)Cu_(6)H_(6),is also competent in catalyzing the hydrogenation of aldehydes such as benzaldehyde and N-methyl-2-pyrrolecarboxaldehyde,albeit accompanied by decomposition pathways.The catalytic performance can be enhanced through the addition of a strong base or^(iPr)PN^(H)P.The three catalytic systems likely share the same catalytically active species,which is proposed to be a mononuclear copper hydride(^(R)PN^(H)P)CuH with the NH group bound to copper.
基金supported by a NTU start-up grant(M4081012)the Nanyang Assistant Professorship(M4081154)+2 种基金an MOE Tier 1 grant(M4011144)The authors acknowledge the support from the Solar Fuels Laboratories at NTU and the Singapore-Berkeley Research Initiative for Sustainable Energy(SinBeRISE)CREATE ProgrammeThis research programme is funded by the National Research Foundation(NRF),Prime Minister’s Office,Singapore under its Campus for Research Excellence and Technological Enterprise(CREATE).H.H.is grateful for the Nanyang Assistant Professorship.
文摘Photovoltaics with dye-sensitized solar cells have been recognized as being promising for the utilization of sunlight to produce electricity and‘solar chemicals’.One of the remaining unsolved challenges is the development of an affordable,robust dye that has a panchromatic light harvesting range and efficiently provides separated charges for the desired photochemistry.The most commonly employed molecular photosensitizers include the noble metal-based ruthenium and iridium complexes,synthetically challenging porphyrin derivatives,and expensive,functionalized polypyridine compounds.Here,we describe the development of Cu(I)dyes supported by bis(arylimino)acenaphthene(Ar-BIAN)ligands,which can be synthesized in fewer than three steps from affordable,commercially available reagents.
基金supported by the National Natural Science Foundation of China(No.21571090)the Liaoning BaiQianWan Talents Program,and the Liaoning Provincial Department of Education Innovation Team Project(LT2017010)We thank the BL17B beamline of the National Facility for Protein Science Shanghai(NFPS)at Shanghai Synchrotron Radiation Facility(SSRF),for assistance with X-ray data collection.
文摘In this study,two copper(II)salts with different configurations,2[H_(3)LCuCl_(4)][Cu_(2)Cl_(6)](1)and[H_(4)L][CuCl_(4)]_(2)Cl(2)(L=(1R,2R)-N,N’-bis(pyridin-4-ylmethyl)cyclohexane-1,2-diamine),have been synthesized and applied in the following solid–gas and solid–solid reactions.Both salts 1 and 2 gave rise to the salt([H_(4)L][Cu_(2)Cl_(8)]H_(2)O(3)upon exposure to HCl gas or grinding with equal moles of CuCl_(2)·2H_(2)O.
文摘Thioether-containing pyridylalkylamide ligands 2-(methylsulfanyl)-N-[2-(pyridine-2-yl)methyl]acetamide(HL1)and 2-(methylsulfanyl)-N-[2-(pyridine-2-yl)ethyl]acetamide(HL2)were synthesized and fully characterized.Three copper complexes{[Cu(L1)(CH3OH)](OTf)}n(1),(OTf=triflate),{[Cu(L2)(OTf)].CH3OH}n(2)and[Cu(HL2)(CH3OH)C1](3)were synthesized and characterized with X-ray diffraction methods.The single-crystal X-ray analyses indicate that complex 1 and 2 form 1D coordination polymers,while complex 3 is a mononuelear copper complex.The coordination modes of the copper ion are analyzed and the reasons are interpreted.CCDC:1421197,1;1421198,2;1421199,3.
文摘Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.
文摘1 Introduction Immobilization of homogeneous catalysts onto polymer supports through covalent attachment has received wide attention because these materials offer advantage features of heterogeneous catalysis to homogeneous systems.The polymer-supported catalysts enhance their thermal stability,selectivity,recyclability and easy separation from reaction products leading to the operationally flexible[1-2].Such behaviour prompted us to know the effect of pore structures of polymer supporters on catalytic ...
文摘Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co（Ⅱ） acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu（Ⅱ） chloride dihydrate in anhydrous methanol. The structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Co3（C51H66N3O16）]2（OAc）, monoclinic, space group P21, a = 15.022（3）, b = 14.242（3）, c = 28.922（6） A, β = 98.944（4）°, V = 6112（2） A3, Z = 4, Dc = 1.339 g/cm^3, the final R = 0.0860 for 21906 observed reflections with I 〉 2（I）. For Ⅱ： Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a = 6.1861（13）, b = 20.838（4）, c = 28.274（6） , V = 3644.6（13） 3, Z = 4, Dc = 1.310 g/cm^3, the final R = 0.0642 for 11106 observed reflections with I 〉 2（I）. The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.
文摘Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.
文摘Introduction Nucleases which catalyze the hydrolytic cleavage of the phosphodiester backbone of DNA and RN A play animportant role in the molecular genetics and genetic engineering.The development of reagents which hydrolytically cleave nucleic acids under mild conditions has currently been attracting great interest in the field of artificial nucleases"",for example,the small metal complexes that promote the hydrolysis of DNA and RNA are useful not only in molecular biology and drug design but also in elucidating the role of metal ions in enzyme catalysis.
基金This work was supported by the Scientific Research Common Program of Beijing Municipal Commission of Education (KM20051028005)
文摘The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1： orthorhombic, space group Pbca with a = 11.921（4）, b = 15.816（6）, c = 17.076（6） A, V= 3219.7（19） A^3, C15H17CuN3O5S, Z = 8, Mr = 414.92, De = 1.712 g/cm^3,μ（MoKα） = 1.520 mm^-1, F（000） = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I 〉 2σ（I）; and crystal data for 2： monoclinic, space group P21/c with a = 7.929（3）, b = 17.038（5）, c = 11.734（4） A, β = 98.162（6）°, V = 1569.1（9） A^3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm^3, F（000） = 820,μ（MoKα） = 1.554 mm^-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections （I 〉 2σ（I））. The molecular structure of complex 1 consists of one tetra-coordinated Cu（Ⅱ） atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper（Ⅱ） structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.
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Modified α and β bis(salicylaldoxime)copper(Ⅱ) have been obtained by recrystallization from ethyl acetate(CCDC Nos. 212157 & 212158). The X-ray analysis reveals that the two modificated forms have the same structure with different geometric parameters. The α form crystallizes in the P2(1)/c space group and the β form in the P1 space group. Both the crystal structures consist of centrosymmetric monomeric molecules of Cu(OC_6H_4CNOH)_2. The IR spectra are in agreement with the structural data.
基金This work was financially supported by Liuhui Center for Applied Mathematics, Nankai and Tianjin Universities (No. H10114)
文摘A flexible double betaine 1,4-bis（pyridinil-4-carboxylato）-1,4-dimethylbenzene L has been used to generate two Cu（Ⅱ）-containing metal complexes that exhibit different polymeric structures： [Cu（H2O）2 L].2NO3 1 and [Cu（H2O）3 L].2Cl.H2O 2. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction method. Crystal data for 1： triclinic, space group PT, a = 5.253（2）, b = 7.406（3）, c = 14.792（5） A, α = 84.195（5）, β = 80.014（5）, γ = 78.053（5）°, V= 553.2（3）A^3, Z = 1, F（000） = 293, Dc = 1.717 g/cm^3, the final R = 0.0385 and wR = 0.1079 for 1883 observed reflections （I 〉 2σ（I））; and those for 2： monoclinic, space group P21/c, a = 10.222（3）, b = 25.287（7）, c = 9.277（3）A, β = 93.572（5）°, V = 2393.2（12）A^3, Z = 4, F（000） = 1140, Dc = 1.540 g/cm^3, the final R = 0.0472 and wR = 0.0956 for 3204 observed reflections （I 〉2o（/））.
基金Supported by the Program for New Century Excellent Talents in University(NCET-10-0176)the Natural Science Foundation of Jilin Province(No.20130521019JH)the fund of Jilin Provincial Education Department of China(No.2014154)
文摘Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.
基金supported by National Natural Science Foundation of China(Nos.21073144,21173169)Fundamental Research Funds for the Central Universities(No.XDJK2013A008)
文摘Computational calculation was performed to investigate the mechanism of trifluoromethylation reactions of iodobenzene with well-defined N-heterocyclic carbene （NHC）-supported Cu~ trifiuor- omethyl complexes. Four proposed reaction pathways, namely cr-bond metathesis （BM）, concerted oxidative addition-reductive elimination （OARE）, iodine atom transfer （IAT） and single-electron transfer （SET）, have been computed by density functional theory （DFT）. The result indicated that the concerted OARE mechanism is favored among the four reaction pathways, suggesting the trifluoromethylation may occur via concerted OARE mechanism involving Ar-X oxidative addition to the Cu（1） center as the rate determining step.
基金Supported by the Natural Science Foundation of China(21671054)the Students Innovative Pilot Plan of Henan University(16NA005)
文摘A couple of chiral mononuclear copper(II)-tyrosine complexes[Cu(L-Tyr)_(2)](1)and[Cu(D-Tyr)_(2)](2)[Tyr=tyrosine]have been successfully synthesized in the aqueous solution and further characterized by elemental analyses,IR spectra,single-crystal X-ray diffraction and circular dichroism(CD)spectroscopy.Structural analysis indicates that 1 and 2 exhibit the interesting 1-D chainlike arrangement architected from the[Cu(L-Tyr)_(2)]or[Cu(D-Tyr)_(2)]units connected by Cu-O linkages.From the view of supramolecular chemistry,neighboring[Cu(L-Tyr)_(2)]or[Cu(D-Tyr)_(2)]units are interlinked through weak hydrogen-bonding interactions constructing the 3-D supramolecular structure.Variable-temperature magnetic susceptibilities of 1 and 2 were investigated,indicating that 1 and 2 exhibit the dominant ferromagnetic behavior.Moreover,the field-dependent magnetization mea-surements suggest that 1 and 2 possess an S=1/2 ground state.
