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1.
Guang-Ri Xu Lu Liu Hui-Ling Gao Jing-Yan Shang 《Journal of Coordination Chemistry》2017,70(15):2684-2694
Reactions of [(μ-SeCH2)2CHC6H5]Fe2(CO)6 (A) with 1,1′-bis(diphenylphosphino)ferrocene (dppf) or 1,3-bis(diphenylphosphino)propane (dppp) in refluxing xylene yielded [(μ-SeCH2)2CHC6H5]Fe2(CO)4(μ-dppf) (1) or [(μ-SeCH2)2CHC6H5]Fe2(CO)4(μ-dppp) (2) in moderate yields. The chemical structures of both complexes were characterized by spectroscopic methods and X-ray crystallography, and the electronic structures were further investigated by UV–vis. The redox properties of both complexes in the absence and presence of acetic acid were observed by cyclic voltammetry (CV). 相似文献
2.
Ge Guo Hui-Ling Gao Feng-Sha Shen Shi-Wei Ge Jing-Yan Shang 《Journal of Coordination Chemistry》2017,70(15):2695-2707
Reaction of 1,2-bis(diphenylphosphino)benzene (dppbz) with PhpdtFe2(CO)6 (A) in hot acetonitrile yielded a chelated complex, PhpdtFe2(CO)4(κ2-dppbz) (1), in moderate yield. Further treatment using an excess of HBF4·Et2O resulted in the protonation of 1 at room temperature in dichloromethane solution, forming a hydride [Phpdt(μ-H)Fe2(CO)4(κ2-dppbz)]BF4 (2). The chemical structures of both complexes were fully characterized by spectroscopic methods and X-ray crystallography, and the electronic structures were further investigated by UV-vis spectroscopy. The cyclic voltammetry (CV) of 1 in the absence and presence of acetic acid were also investigated. 相似文献
3.
《Journal of Coordination Chemistry》2012,65(12):2066-2074
Two N-functionally substituted diiron azadithiolate complexes, [(µ-SCH2)2NCH2CH2OC(O)C6H4I-p]Fe2(CO)6 (1) and {[(µ-SCH2)2NCH2CH2OC(O)C6H4I-p]Fe2(CO)5Ph2PCH}2 (2) as models for the active site of [FeFe] hydrogenases, have been prepared and fully characterized. Complex 1 was prepared by the reaction of [(µ-SCH2)2NCH2CH2OH]Fe2(CO)6 with p-iodobenzoic acid in the presence of 4-dimethylaminopyridine (DMAP) and N,N′-dicyclohexylcarbodiimide (DCC) in 78% yield. Further treatment of 1 with 1 equiv. of Me3NO?·?2H2O followed by 0.5 equiv. of trans-1,2-bis(diphenylphosphino)ethylene (dppe) affords 2 in 60% yield. The new complexes 1 and 2 were characterized by IR and 1H (13C, 31P) NMR spectroscopic techniques and their molecular structures were confirmed by X-ray diffraction analysis. The molecular structure of 1 has two conformational isomers, in one isomer its N-functional substituent is axial to its bridged nitrogen and in the other isomer its N-functional substituent is equatorial. The crystal structure of 2 revealed that its N-functional substituents are equatorial to its nitrogens and dppe occupies the two apical positions of the square-pyramidal irons. 相似文献
4.
《Journal of Coordination Chemistry》2012,65(6):1023-1031
A series of N-functionalized diiron azadithiolate complexes, [(µ-SCH2)2NCH2CO2Me]Fe2(CO)5?L [L?=?CO (1); PPh3 (2); Ph2PCH2PPh2 (3)], as active site models of [FeFe]-hydrogenases has been prepared and characterized. While 1 was prepared by a sequential reaction of (µ-HS)2Fe2(CO)6 with two equiv. of aqueous HCHO, followed by treatment of (µ-HOCH2S)2Fe2(CO)6 with one equiv. of H2NCH2CO2Me in 46% yield; 2 and 3 were prepared by a carbonyl substitution reaction of 1 with PPh3 or Ph2PCH2PPh2 in the presence of Me3NO?·?2H2O in 90% and 85% yields, respectively. The crystal structures of 1 and 2 revealed that the substituent attached to the bridgehead nitrogen occupies an equatorial position and the PPh3 ligand resides in an axial position of the square pyramid of Fe2. 相似文献
5.
Zhiyin Xiao Li Long Giuseppe Zampella Luca De Gioia Qiuyan Luo 《Journal of organometallic chemistry》2010,695(5):721-4107
Reaction of 2-(1-(pyridin-2-yl)ethyl)propane-1,3-dithiol with tri-iron dodecacarbonyl afforded a diiron pentacarbonyl complex, [Fe2L(CO)5] (A and H2L = 2-methyl-2-(1,2,5,6-tetrahydropyridin-2-yl)propane-1,3-dithiol). In the reaction, the pyridinyl ring of the original ligand was partially hydrogenated during the reaction. This complex was fully characterised by using crystallographic, infrared, and NMR spectroscopic techniques. Formation reaction of its bridging hydride and subsequent conversion into its protonated diiron hexacarbonyl complex, [Fe2L(CO)6] (ACOH+ in which the N atom of L is decoordinated and protonated), were experimentally and theoretically investigated. Results for this complex alongside with theoretic investigations into other diiron pentacarbonyl analogues revealed positive correlation of basicity of the internal bases of these investigated complexes to bridging hydrides formation. But subsequent conversion of these bridging hydrides into protonated diiron hexacarbonyl complexes was not solely dictated by the basicity. Protophilicity of the internal base and lability of its coordination with the diiron centre play also an important role as revealed by experimental and theoretic investigations. 相似文献
6.
Hui Li Xiao-Chuan Chai Jie Wang Jun Li Chen-Zhong Yao 《Phosphorus, sulfur, and silicon and the related elements》2020,195(9):747-755
AbstractIn this contribution, two diiron ethane-1,2-dithiolate complexes with one ethyldiphenylphosphine or dicyclohexylphenylphosphine ligand have been synthesized and characterized as mimics for the active site of [FeFe]-hydrogenases. Treatment of complex [Fe2(CO)6(μ-SCH2CH2S)] (1) with ethyldiphenylphosphine or dicyclohexylphenylphosphine and Me3NO · 2?H2O as decarbonylating agent gave complexes [Fe2(CO)5(Ph2PCH2CH3)(μ-SCH2CH2S)] (2) and [Fe2(CO)5{PhP(C6H11)2}(μ-SCH2CH2S)] (3) in 93% and 86% yields, respectively. Complexes 2 and 3 were characterized by elemental analysis, IR, and NMR spectroscopy. X-ray crystallographic studies confirmed the molecular structures of complexes 2 and 3, indicating that they contain a butterfly diiron ethane-1,2-dithiolate cluster with five terminal carbonyl ligands and an apically-coordinated phosphine ligand. Additionally, the electrochemical properties of these complexes were investigated by cyclic voltammetry, suggesting that they can be regarded as electrocatalysts for the reduction of protons to H2 in the presence of HOAc. A possible mechanism for the proton reduction was proposed. 相似文献
7.
《Journal of Coordination Chemistry》2012,65(6):968-979
To investigate the influence of bridgehead-C functionality in diiron dithiolate complexes on the molecular structure and electrocatalytic properties of [FeFe]-hydrogenase models, three new bridgehead-C-functionalized model complexes 1–3 have been synthesized and structurally characterized. Treatments of parent complex [(μ-SCH2)2CHCO2H][Fe2(CO)6] (A) with the esterification agents o-MeC6H4OH, p-ClC6H4OH, or p-HOC6H4CHO in the presence of 4-dimethylaminopyridine and dicyclohexylcarbodiimide in CH2Cl2 at room temperature resulted in formation of [(μ-SCH2)2CHCO2R][Fe2(CO)6] (R = o-MeC6H4–, 1; p-ClC6H4–, 2; p-OHCC6H4–, 3) in 53–55% yields. The new complexes 1–3 were characterized by elemental analysis, IR and NMR spectroscopy, and especially determined by X-ray crystallography. The electrochemical properties of 1–3 and the electrocatalytic H2 evolution catalyzed by 1 have been investigated by cyclic voltammetry, where 1 is a catalyst for HOAc proton reduction to H2 under electrochemical conditions. 相似文献
8.
Xu-Feng Liu 《Journal of Coordination Chemistry》2017,70(1):116-126
Four diiron dithiolate complexes with monophosphine ligands have been prepared and structurally characterized. Reactions of (μ-SCH2CH2S-μ)Fe2(CO)6 or [μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)6 with tris(4-chlorophenyl)phosphine or diphenyl-2-pyridylphosphine in the presence of Me3NO·2H2O afforded diiron pentacarbonyl complexes with monophosphine ligands (μ-SCH2CH2S-μ)Fe2(CO)5[P(4-C6H4Cl)3] (1), (μ-SCH2CH2S-μ)Fe2(CO)5[Ph2P(2-C5H4N)] (2), [μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)5[P(4-C6H4Cl)3] (3), and [μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)5[Ph2P(2-C5H4N)] (4) in good yields. Complexes 1–4 were characterized by elemental analysis, 1H NMR, 31P{1H} NMR and 13C{1H} NMR spectroscopy. Furthermore, the molecular structures of 1–4 were confirmed by X-ray crystallography. 相似文献
9.
Reaction of 1,1′-bis(diphenylphosphino)ferrocene (dppf) with [μ-(SCH2)2NCH2CH2OH]Fe2(CO)6 (A) or [μ-(SCH2)2NCH2CH2SAc]Fe2(CO)6 (C) in refluxing xylene yielded an intramolecular bridging complex [μ-(SCH2)2NCH2CH2OH]Fe2(CO)4(μ-dppf) (1) or [μ-(SCH2)2NCH2CH2SAc]Fe2(CO)4(μ-dppf) (2) in moderate yield. The structures of both complexes were fully characterized by spectroscopic methods and X-ray crystallography, and the electronic structure of 2 was further investigated by UV–vis. The cyclic voltammetry was conducted and the reduction of protons from CF3SO3H (TfOH), HBF4·Et2O, or CF3COOH (TFA) catalyzed by 2 was observed. 相似文献
10.
The reaction of complex [μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)6 (1) with trans-1,2-bis(diphenylphosphino)ethylene (trans-dppv) in the presence of Me3NO?2H2O in CH2Cl2/CH3CN afforded complex {[μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)5}2(trans-dppv) (2) with a bridging dppv. Complex [μ-SCH(CH3)CH(CH3)S-μ]Fe2(CO)4(cis-dppv) (3) was prepared by the reaction of 1 with cis-dppv and Me3NO?2H2O. The new complexes 2 and 3 were characterized by elemental analysis, spectroscopy, and X-ray diffraction analysis. 相似文献
11.
In order to improve the hydro- and protophilicity of the active site models of the Fe-only hydrogenases, three diiron dithiolate complexes with DAPTA ligand(s) (DAPTA = 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane), (μ-pdt)[Fe(CO)3][Fe(CO)2(DAPTA)] (1, pdt = 1,3-propanedithiolato), (μ-pdt)[Fe(CO)2(DAPTA)]2 (2) and (μ-pdt)[Fe(CO)2(PTA)][Fe(CO)2(DAPTA)] (3), were prepared and spectroscopically characterized. The water solubility of DAPTA-coordinate complexes 1-3 is better than that of the PTA-coordinate analogues. With complexes 1-3 as electrocatalysts, the overvoltage is reduced by 460-770 mV for proton reduction from acetic acid at low concentration in CH3CN. Significant decrease, up to 420 mV, in reduction potential for the Fe(I)Fe(I) to Fe(I)Fe(0) process and the curve-crossing phenomenon are observed in cyclic voltammograms of 2 and 3 in CH3CN/H2O mixtures. The introduction of the DAPTA ligand to the diiron dithiolate model complexes indeed makes the water solubility of 2 and 3 sufficient for electrochemical studies in pure water, which show that the proton reduction from acetic acid in pure water is electrochemically catalyzed by 2 and 3 at ca. −1.3 V vs. NHE. 相似文献
12.
Xu-Feng Liu 《Journal of Coordination Chemistry》2016,69(17):2620-2629
Four diiron toluenedithiolate complexes 2–5 with monophosphine ligands are reported. Treatment of [μ-SC6H3(CH3)S-μ]Fe2(CO)6 (1) with tris(3-chlorophenyl)phosphine, tris(4-chlorophenyl)phosphine, tris(4-methylphenyl)phosphine or 2-(diphenylphosphino)benzaldehyde, and Me3NO?2H2O in MeCN resulted in the formation of [μ-SC6H3(CH3)S-μ]Fe2(CO)5[P(3-C6H4Cl)3] (2), [μ-SC6H3(CH3)S-μ]Fe2(CO)5[P(4-C6H4Cl)3] (3), [μ-SC6H3(CH3)S-μ]Fe2(CO)5[P(4-C6H4CH3)3] (4), and [μ-SC6H3(CH3)S-μ]Fe2(CO)5[Ph2P(2-C6H4CHO)] (5) in 64–82% yields. Complexes 2–5 have been characterized by elemental analysis, IR, 1H NMR, 31P{1H} NMR, 13C{1H} NMR and further confirmed by single crystal X-ray diffraction analysis. The molecular structures show that 2–5 contain a butterfly diiron toluenedithiolate cluster coordinated by five terminal carbonyls and an apical monophosphine. 相似文献
13.
《Journal of Coordination Chemistry》2012,65(15):2531-2543
AbstractIn this article, five diiron 1,2-dithiolate complexes containing phosphine ligands are reported. Treatment of complex [Fe2(CO)6(μ-SCH2CH2S)] (1) with the phosphine ligands tris(4-methylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(3-chlorophenyl)phosphine, tris(3-methylphenyl)phosphine, or 2-(diphenylphosphino)biphenyl in the presence of Me3NO·2H2O as the decarbonylating agent afforded the target products [Fe2(CO)5(L)(μ-SCH2CH2S)] [L?=?P(4-C6H4CH3)3, 2; P(4-C6H4OCH3)3, 3; P(3-C6H4Cl)3, 4; P(3-C6H4CH3)3, 5; Ph2P(2-C6H4Ph), 6] in 80–93% yields. Complexes 2–6 have been characterized by elemental analysis, spectroscopy, and X-ray crystallography. Additionally, the electrochemical properties were studied by cyclic voltammetry. 相似文献
14.
《印度化学会志》2021,98(4):100049
The new azo-imine ligands 2,4-di-tert-butyl-6-((2-((2-hydroxyphenyl)diazenyl) phenylimino)methyl)phenol, H2L1, 1a, and 2,4-di-tert-butyl-6-((2-((2-hydroxyphenyl) diazenyl)p-chlorophenylimino)phenol, H2L2, 1b, were prepared. Reaction of H2L1;1a, and H2L2;1b, with uranyl nitrate hexahydrate afforded the mononuclear complexes of compositions [U(O)2(L1)(H2O)]; 2a, and [U(O)2(L2)(H2O)]; 2b, complexes respectively. The newly synthesised ligands (1a and 1b) and the complexes (2a and 2b) were characterised unequivocally. The x-ray structure of 2a was determined. The tetradentate dianionic ligand (L1)2- coordinated the uranium ion equatorially with a water molecule in the same plane. Two axially coordinated oxo ligands completed the overall pentagonal bipyramid geometry around U(VI) ion. Structural pattern, electron transfer properties (oxidation near 1.32 V vs Ag/AgCl) and electronic transitions of [U(O)2(L1)(H2O)]; 2a, and [U(O)2(L2)(H2O)]; 2b have been rationalized by DFT calculations. 相似文献
15.
Hassan Hadadzadeh Ali R. Rezvani Francine Belanger-Gariepy 《Journal of Molecular Structure》2005,740(1-3):165-168
Several new RhIII complexes, [Rh(tpy)(bpy)L](PF6)2 (tpy=2,2′:6′,2″-terpyridine, bpy=2,2′-bipyridine, and L=monoanions of phenylcyanamide(pcyd)), 4-methylphenylcyanamide (4-MePcyd), 2,4-dimethylphenylcyanamide (2,4-Me2pcyd), 4-methoxyphenylcyanamide (4-MeOPcyd), 2-chlorophenylcyanamide (2-Clpcyd) and 2,5-dichlorophenylcyanamide (2,5-Cl2pcyd) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic absorption spectroscopies. ORTEP drawing of [Rh(tpy)(bpy)(2,5-Cl2pcyd)](PF6)2·1/2CH3CN shows three pyridyl rings of the tpy ligand that are nearly coplanar, as are the two rings of bpy. The anionic cyanamide group is coordinated end-on by the nitrile nitrogen to the RhIII. The RhIII–NCN bond is bent, having an angle of 125.4°. This bent bond is largely determined by the σ-bonding interaction of a cyanamide non-bonding electron pair in a sp2 hybrid orbital. 相似文献
16.
本文报道了4个含膦配体二铁二硫五羰基配合物的合成和结构表征。起始配合物[Fe2(CO)6(μ-SCH2CH (CH2OOCH) S)](1)与三苯基膦、三环己基膦、三(2-甲氧基苯基)膦或三(4-三氟甲基苯基)膦和脱羰试剂Me3NO·2H2O反应,以59%~88%的产率制备了目标产物[Fe2(CO)5(L)(μ-SCH2CH (CH2OOCH) S)](L=PPh3(2)、PCy3(3)、P (2-C6H4OCH3)3(4)、P (4-C6H4CF3)3(5))。配合物2~5以元素分析、红外光谱、核磁共振以及单晶X射线衍射进行了表征。电化学性质研究表明配合物1~5均可以实现电化学催化质子还原产生氢气的功能,其中配合物1的催化产氢效率明显优于其它配合物。 相似文献
17.
《Journal of Coordination Chemistry》2012,65(6):975-986
Three new complexes, [Ni2(dpc)2(L1)2(H2O)2]?·?4H2O (1), [Ni(dpc)(L2)1.5] n (2), and {[Ni(dpc)(L3)1.5]?·?2H2O} n (3), where H2dpc?=?dipicolinic acid, L1?=?1,4-bis(2-methylimidazol-1-yl)butane, L2?=?4,4′-bis(2-methylimidazol-1-ylmethyl)biphenyl, and L3?=?1,4-bis(benzimidazol-1-yl)-2-butylene, have been synthesized by hydrothermal methods and characterized by elemental analyses, infrared spectra, thermogravimetric analysis, and X-ray crystallography. The common structural characteristic of the three complexes is that the Ni2+ is coordinated by tridentate dipicolinate through nitrogen of pyridine and oxygen of carboxylate, serving as a terminal ligand. In 1, two L1 link two [Ni(dpc)(H2O)] units to a discrete binuclear metallomacrocycle with a 22-membered ring, which is assembled through multiple O–H?···?O hydrogen bonds to form a 3-D supramolecular framework. Complex 2 exhibits a 1-D ladder-like chain structure constructed by cis/trans-conformation L2 linking metal centers; 3 displays a 2-D (6,3) topology, being constructed from the linking of [Ni(pdc)] by L3. These results indicate the merits of flexible bis(imidazole) ligands as building blocks with dipicolinate for the construction of complexes with diverse structural motifs. 相似文献
18.
《Journal of Coordination Chemistry》2012,65(19):3402-3411
Three coordination complexes with N-donor ligands, Ag2(L1)1.5(NO3)2 (1), Ag3(L2)2(NO3)3 (2), and Ag(L1)2NO3 (3) {L1?=?1,4-bis(pyrazole-1-ylmethyl)benzene, L2 = 4,4′-bis(pyrazole-1-ylmethyl)biphenyl}, have been synthesized and structurally characterized by elemental analysis, IR spectroscopy, TGA, and X-ray single crystal diffraction. Complex 1 shows a 3-D fsh-3,4-P21/c structure with brevity code {83}2{85·10}. Complex 2 has a 3-D framework with a 2-D layer penetrated by an infinite 1-D zigzag chain. Complex 3 exhibits a (4,4)-net racemizing layer structure with nitrate anions filling the cavity. The results indicate that L1 and L2 can adopt varied conformations in formation of the complexes, and the length of the ligands plays a key role in configuring and directing the corresponding structure of the complexes. 相似文献
19.
《Journal of Coordination Chemistry》2012,65(6):1022-1031
Two new structurally similar molybdenum(VI) complexes, [MoO2L1(CH3OH)] (1) and [MoO2L2(CH3OH)] (2), where L1 is the dianionic form of N′-(2-hydroxy-5-nitrobenzylidene)-2-methylbenzohydrazide and L2 is the dianionic form of N′-(2-hydroxy-4-methoxybenzylidene)-2-methylbenzohydrazide, were prepared and structurally characterized by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. 1 crystallizes in the monoclinic space group P21/c, with unit cell dimensions a?=?7.941(1), b?=?14.337(2), c?=?15.141(2)?Å, β?=?92.782(2)°, V?=?1721.8(4)?Å3, Z?=?4, R1?=?0.0286, wR2?=?0.0650, GOOF?=?1.028. 2 crystallizes in the triclinic space group P-1, with unit cell dimensions a?=?8.003(1), b?=?10.608(1), c?=?10.880(1)?Å, α?=?95.745(2)°, β?=?97.627(2)°, γ?=?105.762(2)°, V?=?872.0(2)?Å3, Z?=?2, R1?=?0.0226, wR2?=?0.0595, GOOF?=?1.116. X-ray analysis indicates that Mo in the complexes are coordinated by the phenolate oxygen, imino nitrogen, and enolate oxygen of the benzohydrazone, methanol, and two oxo groups, generating octahedral coordination. The oxidation of olefins with the complexes as catalysts was evaluated, indicating that the complexes showed excellent catalytic efficiency in oxidation of most aliphatic and aromatic substrates under mild conditions using tert-butyl hydrogen peroxide as oxidant. 相似文献