以Fe(CO)_(5)和含一个巯基的配体为原料,通过多步反应合成了两个新的[FeFe]氢化酶模拟物1和2;构建了以化合物1和2为光催化剂、藻红B钠盐(EBS^(2-))为光敏剂、三乙胺(TEA)为电子给体和质子源的三组分光催化产氢体系,该体系在pH值为12且...以Fe(CO)_(5)和含一个巯基的配体为原料,通过多步反应合成了两个新的[FeFe]氢化酶模拟物1和2;构建了以化合物1和2为光催化剂、藻红B钠盐(EBS^(2-))为光敏剂、三乙胺(TEA)为电子给体和质子源的三组分光催化产氢体系,该体系在pH值为12且体积比为1∶1的CH_(3)CN/H_(2)O溶液中,经可见光(λ>420 nm)照射4 h,最大产氢量为205.0μmol,相对于化合物2的催化转化数(TON)为51.4;研究表明,配体中含有较多的质子捕获位点,有利于形成产氢活性中间体H 2-2Fe2S(η2-H 2-Fe II Fe I)物种,从而提高催化剂的产氢活性,光生电子从1*EBS^(2-)化合物1和2的第一个电子的转移均为热力学可行过程,到化合物1和2的第二个电子转移是热力学不可行过程。展开更多
Two new diiron ethanedithiolate complexes Fe2（S2C2H4）（CO）5（2-Ph2PC6H4NH2） （1） and Fez（S2CzH4）（CO）5（2-PhzPC6H4CHzNH2） （2） as active site models of [FeFe] hydrogenases have been prepared by the treatment...Two new diiron ethanedithiolate complexes Fe2（S2C2H4）（CO）5（2-Ph2PC6H4NH2） （1） and Fez（S2CzH4）（CO）5（2-PhzPC6H4CHzNH2） （2） as active site models of [FeFe] hydrogenases have been prepared by the treatment of （,u-SCHzCH2S-μ）Fe2（CO）6 with 2-PhzPC6H4NH2 or 2-PhzPC6H4CH2NH2 in the presence of the decarbonylating agent Me3NO＇2H20. As new complexes, both 1 and 2 were fully characterized by elemental analysis, IR and^1H （13C, 31p） NMR spectroscopies. In addition, the molecular structure of complex 1 was established by X-ray crystallography. The crystal of Fe2（S2C2H4）（CO）5（2-PhzPC6H4NH2） （1） crystallizes in orthorhombic, spacegroup Pna21 with a = 20.9461（17）, b = 13.7615（11）, c = 9.3133（7）A, V= 2684.6（4） A3, Z = 4, C25Hz0FezNOsPS2, Mr = 621.21, Dc = 1.537 g/cm^3, F（000） = 1264. The final R = 0.0197 and wR = 0.0495 for 4605 observed reflections with I 〉 2a（/） and R = 0.0206 and wR = 0.0501 for all data.展开更多
The reaction of [Fe2S2（CO）6] with one equiv.of o-OCH3C6H4CH2Br under the re-duction of LiBHEt3 in dry THF afforded a tetranuclear cluster [（μ4-S）{（μ-SCH2（o-OCH3）Ph）Fe2（CO）6}2]（1）.Complex 1 crystallizes i...The reaction of [Fe2S2（CO）6] with one equiv.of o-OCH3C6H4CH2Br under the re-duction of LiBHEt3 in dry THF afforded a tetranuclear cluster [（μ4-S）{（μ-SCH2（o-OCH3）Ph）Fe2（CO）6}2]（1）.Complex 1 crystallizes in monoclinic,space group P21/n with a = 16.5623（6）,b = 12.8265（5）,c = 18.2702（7） ,β = 115.95（1）o,V = 3489.9（4） 3,Z = 4,μ = 1.87 mm-1,Dc = 1.709 Mg/m3,T = 296（2） K,C28H18Fe4O14S3,Mr = 898.03,F（000） = 1800,S = 1.10,R = 0.032 and wR = 0.058.Complex 1 consists of two diiron fragments possessing a {Fe2（CO）6} core.The two diiron units are bridged by an inorganic sulfide in a μ4-S binding mode and the sulfide is in a distorted tetrahedral geometry with the four iron atoms at each corner of the distorted tetrahedral.In its solid state,two types of non-classic intermolecular hydrogen bonding interactions plus a weak π-π stacking interaction led to a 2-D network.展开更多
Two diiron dithiolate complexes, （μ-pdt）Fe2（CO）5（C7H10N2） 3 and （μ-edt）-Fe2（CO）5（C7H10N2） 4 （pdt = -S（CH2）3S-, edt = -S（CH2）2S-）, have been synthesized and characterized by single-crystal X-ray dif...Two diiron dithiolate complexes, （μ-pdt）Fe2（CO）5（C7H10N2） 3 and （μ-edt）-Fe2（CO）5（C7H10N2） 4 （pdt = -S（CH2）3S-, edt = -S（CH2）2S-）, have been synthesized and characterized by single-crystal X-ray diffraction. Complex 3 crystallizes in the monoclinic system, space group P21/c with a = 10.168（4）, b = 11.816（4）, c = 16.595（7） and β = 95.195（6）o; and complex 4 crystallizes in the orthorhombic system, space group P212121 with a = 9.317（3）, b = 11.898（4）, c = 34.006（10） .The distances of Fe（1）–Fe（2） are 2.5058（9） in 3 and 2.4942（10） in 4, falling in the normal range of Fe–Fe bond length （2.49～2.57 ）. The cyclic voltammograms show that 3 and 4 display irreversible reduction peaks （FeIFeI/ FeIFe0） at –1.717 V and –1.673 V vs. Ag/AgCl, respectively. With different acids, complex 3 has distinguishable behavior, two protonations in addition of HBF4-Et2O and single protonation besides HOAc-CH3CN, and complex 4 has a similar action to 3 with HOAc-CH3CN for a semblable structure.展开更多
A new 2Fe2 S complex[（2-C5H4N）N（μ-CH2S）2Fe2（CO）6]（1） related to the active site of[FeFe]-hydrogenase was obtained by treating（HS）2Fe2（CO）6 with（pyridin-2-ylazanediyl）dimethanol.Protonation occurred at t...A new 2Fe2 S complex[（2-C5H4N）N（μ-CH2S）2Fe2（CO）6]（1） related to the active site of[FeFe]-hydrogenase was obtained by treating（HS）2Fe2（CO）6 with（pyridin-2-ylazanediyl）dimethanol.Protonation occurred at the pyridine nitrogen atom when two equivalents of HBF4·OEt2acid were added to the toluene solution of 1,leading to the formation of[（2-C5H4NH）N（μ-CH2S）2Fe2（CO）6]·BF4·OEt2（1H~＋）,whose molecular structure was further established by singlecrystal X-ray analysis.Complex 1 crystallizes in the monoclinic system,space group P21/n with α=7.728（3）,b = 11.825（4）,c = 17.888（6） A,β= 92.968（5）°,while complex 1H~＋ crystallizes in the triclinic system,space group P1 with a = 7.672（4）,b = 10.382（5）,c = 16.480（10） A,α=106.575（13）,β= 93.18（3）,γ=104.262（17）°.展开更多
A pyrazole-substituted diiron dithiolate complex [Fez（p-pdt）（CO）5（3,5-Me2Pz）] （1, 3,5-MezPz = 3,5-dimethylpyrazole） was prepared as a biomimetic model for the active site of [FeFe]-hydrogenase by CO-substituti...A pyrazole-substituted diiron dithiolate complex [Fez（p-pdt）（CO）5（3,5-Me2Pz）] （1, 3,5-MezPz = 3,5-dimethylpyrazole） was prepared as a biomimetic model for the active site of [FeFe]-hydrogenase by CO-substitution of aU-carbonyl complex [Fe2（μ-pdt）（CO）6] with 3,5-Me2Pz. The molecular structure was confirmed by MS, IR, 1H NMR, elemental analysis and single-crystal X-ray analysis. Complex 1 crystallizes in the triclinic system, space group PI with a = 9.108（7）, b = 9.743（8）, c = 11.192（9）A, a = 109.235（5）, fl = 101.914（9）, y = 96.605（6）. In CH3CN solution, reversible transformation between 1 and the acetonitrile-substituted species [Fe2（p-pdt）- （CO）5（NCCH3）] was detected by both IR and cyclic voltammetry （CV）. The electrochemical proton reduction catalyzed by 1 in the presence of acetic acid was also studied in CH2C12.展开更多
The catalytic generation of H_(2) in living cells provides a method for antioxidant therapy.In this study,an[FeFe]-hydrogenase mimic[Ru+Fe_(2)S_(2)@F127(80)]was synthesized by self-assembling polymeric pluronic F-127,...The catalytic generation of H_(2) in living cells provides a method for antioxidant therapy.In this study,an[FeFe]-hydrogenase mimic[Ru+Fe_(2)S_(2)@F127(80)]was synthesized by self-assembling polymeric pluronic F-127,catalytic[Fe_(2)S_(2)]sites,and photosensitizer Ru(bpy)_(3)^(2+).Under blue light irradiation,hydrated protons were photochemically reduced to H2,which increased the local pH in living cells(HeLa cells).The generated H2 was subsequently used as an antioxidant to decrease reactive oxygen species(ROS)levels in living cells(HEK 293T,HepG2,MCF-7,and HeLa cells).Our findings revealed that the proliferation of HEK 293T cells increased by a factor of about six times,relative to that of other cells(HepG2,MCF-7,and HeLa cells).Intracellular ROS and pH levels were then monitored using fluorescent cell imaging.Our study showed that cell imaging can be used to evaluate the ability of Ru t Fe2S2@F127 to eliminate oxidative stress and prevent ROS-related diseases.展开更多
In this paper,a novel diiron ethane-1,2-dithiolate complex[Fe2(CO)4{κ2-(Ph2P)2(1,2-C6H4)}(μ-SCH2CH2S)]has been prepared and structurally characterized.Treatment of the parent complex[Fe2(CO)6(μ-SCH2CH2S)]with 1 equ...In this paper,a novel diiron ethane-1,2-dithiolate complex[Fe2(CO)4{κ2-(Ph2P)2(1,2-C6H4)}(μ-SCH2CH2S)]has been prepared and structurally characterized.Treatment of the parent complex[Fe2(CO)6(μ-SCH2CH2S)]with 1 equivalent of 1,2-bis(diphenylphosphino)benzene and Me3NO?2H2O as the oxidative agent gave the title complex in good yield.The title complex has been characterized by elemental analysis,IR,1H NMR,31P{1H}NMR,13C{1H}NMR spectroscopy,and X-ray crystallography.X-ray crystal structure of the title complex contains a butterfly diiron cluster with a bridging ethane-1,2-dithiolate,four terminal carbonyls,and a chelating 1,2-bis(diphenylphosphino)benzene.In addition,electrochemical studies revealed that the title complex can catalyze the reduction of protons to H2 in the presence of acetic acid.展开更多
文摘以Fe(CO)_(5)和含一个巯基的配体为原料,通过多步反应合成了两个新的[FeFe]氢化酶模拟物1和2;构建了以化合物1和2为光催化剂、藻红B钠盐(EBS^(2-))为光敏剂、三乙胺(TEA)为电子给体和质子源的三组分光催化产氢体系,该体系在pH值为12且体积比为1∶1的CH_(3)CN/H_(2)O溶液中,经可见光(λ>420 nm)照射4 h,最大产氢量为205.0μmol,相对于化合物2的催化转化数(TON)为51.4;研究表明,配体中含有较多的质子捕获位点,有利于形成产氢活性中间体H 2-2Fe2S(η2-H 2-Fe II Fe I)物种,从而提高催化剂的产氢活性,光生电子从1*EBS^(2-)化合物1和2的第一个电子的转移均为热力学可行过程,到化合物1和2的第二个电子转移是热力学不可行过程。
基金supported by Science & Technology Department of Sichuan Province (2011JY0052,2012JY0115, 2010GZ0130)Sichuan University of Science & Engineering (2011RC06, 2012PY04, 2012PY14)
文摘Two new diiron ethanedithiolate complexes Fe2（S2C2H4）（CO）5（2-Ph2PC6H4NH2） （1） and Fez（S2CzH4）（CO）5（2-PhzPC6H4CHzNH2） （2） as active site models of [FeFe] hydrogenases have been prepared by the treatment of （,u-SCHzCH2S-μ）Fe2（CO）6 with 2-PhzPC6H4NH2 or 2-PhzPC6H4CH2NH2 in the presence of the decarbonylating agent Me3NO＇2H20. As new complexes, both 1 and 2 were fully characterized by elemental analysis, IR and^1H （13C, 31p） NMR spectroscopies. In addition, the molecular structure of complex 1 was established by X-ray crystallography. The crystal of Fe2（S2C2H4）（CO）5（2-PhzPC6H4NH2） （1） crystallizes in orthorhombic, spacegroup Pna21 with a = 20.9461（17）, b = 13.7615（11）, c = 9.3133（7）A, V= 2684.6（4） A3, Z = 4, C25Hz0FezNOsPS2, Mr = 621.21, Dc = 1.537 g/cm^3, F（000） = 1264. The final R = 0.0197 and wR = 0.0495 for 4605 observed reflections with I 〉 2a（/） and R = 0.0206 and wR = 0.0501 for all data.
基金supported by the Education Department of Jiangxi Province (GJJ11033)
文摘The reaction of [Fe2S2（CO）6] with one equiv.of o-OCH3C6H4CH2Br under the re-duction of LiBHEt3 in dry THF afforded a tetranuclear cluster [（μ4-S）{（μ-SCH2（o-OCH3）Ph）Fe2（CO）6}2]（1）.Complex 1 crystallizes in monoclinic,space group P21/n with a = 16.5623（6）,b = 12.8265（5）,c = 18.2702（7） ,β = 115.95（1）o,V = 3489.9（4） 3,Z = 4,μ = 1.87 mm-1,Dc = 1.709 Mg/m3,T = 296（2） K,C28H18Fe4O14S3,Mr = 898.03,F（000） = 1800,S = 1.10,R = 0.032 and wR = 0.058.Complex 1 consists of two diiron fragments possessing a {Fe2（CO）6} core.The two diiron units are bridged by an inorganic sulfide in a μ4-S binding mode and the sulfide is in a distorted tetrahedral geometry with the four iron atoms at each corner of the distorted tetrahedral.In its solid state,two types of non-classic intermolecular hydrogen bonding interactions plus a weak π-π stacking interaction led to a 2-D network.
基金Supported by the National Natural Science Foundation of China (No. 20973172, 21071145)the National Basic Research Program of China (No. 2009CB220009)
文摘Two diiron dithiolate complexes, （μ-pdt）Fe2（CO）5（C7H10N2） 3 and （μ-edt）-Fe2（CO）5（C7H10N2） 4 （pdt = -S（CH2）3S-, edt = -S（CH2）2S-）, have been synthesized and characterized by single-crystal X-ray diffraction. Complex 3 crystallizes in the monoclinic system, space group P21/c with a = 10.168（4）, b = 11.816（4）, c = 16.595（7） and β = 95.195（6）o; and complex 4 crystallizes in the orthorhombic system, space group P212121 with a = 9.317（3）, b = 11.898（4）, c = 34.006（10） .The distances of Fe（1）–Fe（2） are 2.5058（9） in 3 and 2.4942（10） in 4, falling in the normal range of Fe–Fe bond length （2.49～2.57 ）. The cyclic voltammograms show that 3 and 4 display irreversible reduction peaks （FeIFeI/ FeIFe0） at –1.717 V and –1.673 V vs. Ag/AgCl, respectively. With different acids, complex 3 has distinguishable behavior, two protonations in addition of HBF4-Et2O and single protonation besides HOAc-CH3CN, and complex 4 has a similar action to 3 with HOAc-CH3CN for a semblable structure.
基金supported by the National Basic Research Program of China(973 Program2012CB821702)+1 种基金the National Natural Science Foundation of China(21233009 and 21173221)the State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences
文摘A new 2Fe2 S complex[（2-C5H4N）N（μ-CH2S）2Fe2（CO）6]（1） related to the active site of[FeFe]-hydrogenase was obtained by treating（HS）2Fe2（CO）6 with（pyridin-2-ylazanediyl）dimethanol.Protonation occurred at the pyridine nitrogen atom when two equivalents of HBF4·OEt2acid were added to the toluene solution of 1,leading to the formation of[（2-C5H4NH）N（μ-CH2S）2Fe2（CO）6]·BF4·OEt2（1H~＋）,whose molecular structure was further established by singlecrystal X-ray analysis.Complex 1 crystallizes in the monoclinic system,space group P21/n with α=7.728（3）,b = 11.825（4）,c = 17.888（6） A,β= 92.968（5）°,while complex 1H~＋ crystallizes in the triclinic system,space group P1 with a = 7.672（4）,b = 10.382（5）,c = 16.480（10） A,α=106.575（13）,β= 93.18（3）,γ=104.262（17）°.
基金supported by the National Basic Research Program of China(973Program,2012CB821702)the National Natural Science Foundation of China(21173221and20903096)the State Key Laboratory of Structural Chemistry(20120015)
文摘A pyrazole-substituted diiron dithiolate complex [Fez（p-pdt）（CO）5（3,5-Me2Pz）] （1, 3,5-MezPz = 3,5-dimethylpyrazole） was prepared as a biomimetic model for the active site of [FeFe]-hydrogenase by CO-substitution of aU-carbonyl complex [Fe2（μ-pdt）（CO）6] with 3,5-Me2Pz. The molecular structure was confirmed by MS, IR, 1H NMR, elemental analysis and single-crystal X-ray analysis. Complex 1 crystallizes in the triclinic system, space group PI with a = 9.108（7）, b = 9.743（8）, c = 11.192（9）A, a = 109.235（5）, fl = 101.914（9）, y = 96.605（6）. In CH3CN solution, reversible transformation between 1 and the acetonitrile-substituted species [Fe2（p-pdt）- （CO）5（NCCH3）] was detected by both IR and cyclic voltammetry （CV）. The electrochemical proton reduction catalyzed by 1 in the presence of acetic acid was also studied in CH2C12.
基金supported by the National Natural Science Foundation of China(Grant No.:21705165)the Open Project Program of the MOE Key Laboratory of Drug Quality Control and Pharmacovigilance(Grant No.:DQCP20/21MS03)the Priority Academic Program Development of Jiangsu Higher Education Institutions,and"Double First-Class"University Project(Grant No.:CPU2018GF07).
文摘The catalytic generation of H_(2) in living cells provides a method for antioxidant therapy.In this study,an[FeFe]-hydrogenase mimic[Ru+Fe_(2)S_(2)@F127(80)]was synthesized by self-assembling polymeric pluronic F-127,catalytic[Fe_(2)S_(2)]sites,and photosensitizer Ru(bpy)_(3)^(2+).Under blue light irradiation,hydrated protons were photochemically reduced to H2,which increased the local pH in living cells(HeLa cells).The generated H2 was subsequently used as an antioxidant to decrease reactive oxygen species(ROS)levels in living cells(HEK 293T,HepG2,MCF-7,and HeLa cells).Our findings revealed that the proliferation of HEK 293T cells increased by a factor of about six times,relative to that of other cells(HepG2,MCF-7,and HeLa cells).Intracellular ROS and pH levels were then monitored using fluorescent cell imaging.Our study showed that cell imaging can be used to evaluate the ability of Ru t Fe2S2@F127 to eliminate oxidative stress and prevent ROS-related diseases.
基金supported by the Natural Science Foundation of Zhejiang Province(LY19B020002)National Natural Science Foundation of China(21501124)+2 种基金Science&Technology Department of Sichuan Province(2018JY0235)Education Department of Sichuan Province(18ZA0337)Sichuan University of Science&Engineering(S201910622022)。
文摘In this paper,a novel diiron ethane-1,2-dithiolate complex[Fe2(CO)4{κ2-(Ph2P)2(1,2-C6H4)}(μ-SCH2CH2S)]has been prepared and structurally characterized.Treatment of the parent complex[Fe2(CO)6(μ-SCH2CH2S)]with 1 equivalent of 1,2-bis(diphenylphosphino)benzene and Me3NO?2H2O as the oxidative agent gave the title complex in good yield.The title complex has been characterized by elemental analysis,IR,1H NMR,31P{1H}NMR,13C{1H}NMR spectroscopy,and X-ray crystallography.X-ray crystal structure of the title complex contains a butterfly diiron cluster with a bridging ethane-1,2-dithiolate,four terminal carbonyls,and a chelating 1,2-bis(diphenylphosphino)benzene.In addition,electrochemical studies revealed that the title complex can catalyze the reduction of protons to H2 in the presence of acetic acid.
