Syntheses and Characterization of Two Diiron Dithiolate Complexes Containing 4-Dimethylaminopyridine

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.     

Emissive Annular Digold(I) Compounds Containing Diphosphine and Dithiolate Ligands

Molecular structures of three emissive annular digold compounds [Au₂(dmpm)(dtc)]Cl (dmpm = Me₂PCH₂PMe_2,dtc = S₂CNEt₂), 1 , [Au₂(dppm)(dtc)]PF₆, (dppm = Ph₂PCH₂PPh₂),₂,and [Au₂(dppe)(dtc)]-(PF₂) (dppe = Ph₂P(CH₂)₂PPh₂), 3, were determined. All three compounds are dimetallacycles having two gold atoms bridged by a dithiolate ligand and a diphosphine ligand, the geometry around each gold atom being almost linear. All the dimetal lacy die rings are slightly distorted from planarity with intramolecular Au-Au distances shorter than 3.0 Å. Compound 1 forms a polymeric chain through intermolecular Au-Au contacts (3.061 ? 3.135 Å). Compound 2 forms a tetramer through intermolecular Au-Au interactions (Au-Au distances ranging from 3.086 to 3.222 ). Compound 3 is monomeric. All of the compounds luminesce at 77 K in the solid state. Emissions originating from ³LMCT from dtc ligand to Au excited states are assigned. The emission maxima of 1 ? 3 are at 541,535 and 520 nm respectively and are blue shifted as the number of Au-Au interactions is decreased.     

Synthesis,Characterization, and Crystal Structures of Diruthenium Complexes Containing Bridging Salicylato Ligands

The thermal reaction of Ru₃(CO)₁₂ ( 1 ) with salicylic acid, in the presence of triphenylphosphine, pyridine, or dimethylsulfoxide, afforded the dinuclear complexes Ru₂(CO)₄(μ‐O₂CC₆H₄OH)₂L₂ ( 2 ) [L = PPh₃ ( 2a ). C₅H₅N ( 2b ); (CH₃)₂SO ( 2c )]. Complex 2b was further reacted with the aromatic dimmines 2,2′‐dipyridine or 1,10‐phenanthroline to give the cationic diruthenium complexes [Ru₂(CO)₂(μ‐CO)₂(μ‐O₂CC₆H₄OH)(N∩N)₂]⁺ ( 3 ) [(N∩N) = 2,2′‐dipyridine ( 3a ); 1,10‐phenanthroline ( 3b )], which were isolated as their tetraphenylborate salts. All five novel complexes were characterized spectroscopically and analytically. For 2a – 2b and 3a – 3b , single‐crystal X‐ray diffraction studies were also carried out.     

新型含氮配体多核铜配合物的合成、晶体结构及其性能研究

以1,10-邻菲罗啉(phen)为配体,采用溶剂蒸发法在水中分别合成了羟基桥连和氯离子桥连的两个新型的含氮配体多核铜离子配合物[Cu4(phen)4(H2O)2(OH)4·(NO3)4·2H2O(1)和Cu2(phen)2Cl4(2)],其结构经元素分析和X-射线单晶衍射表征。1属三斜晶系,空间群P-1,晶胞参数a=10.143 0(9),b=11.900 1(11),c=12.629 9(13),α=111.060(2)°,β=91.070 0(10)°,γ=110.920(2)°,Z=1,V=1 309.8(2)3,F(000)=692。2属单斜晶系,空间群Cc,晶胞参数a=9.860 9(8),b=17.852 9(13),c=13.412 3(15),β=106.583(11)°,Z=4,V=2 263.0(4)3,F(000)=1 256。用荧光光谱和热分析分别研究了1和2的荧光性质和热稳定性,结果表明:在310 nm激发波长激发下,与phen相比,1和2的荧光发射峰分别发生红移和蓝移,λem分别位于451 nm和374 nm。1和2的初始分解温度分别为298℃和300℃。     

两个单核镍含氮配体配合物的合成、晶体结构及荧光性质

采用回流法在水溶剂中合成了2个含氮配体单核镍配合物[Ni（phen）₂（H₂O）₂]（1,6-nds）·2H₂O（1）和[Ni（phen）₃]（1,6-nds）·10H₂O（2）（1,6-nds=1,6-萘二磺酸根离子,phen=1,10-邻菲罗啉）。配合物1中,镍离子与2个1,10-邻菲罗啉和2个水分子配位,形成[Ni（phen）₂（H₂O）₂]²⁺阳离子。2个没有配位的水分子通过氢键与[Ni（phen）₂（H₂O）₂]²⁺和1,6-萘二磺酸根离子相互连接形成二维层状结构。配合物2中,镍离子与3个1,10-邻菲罗啉配位,形成[Ni（phen）₃]²⁺阳离子。大量的氢键将自由的水分子和1,6-萘二磺酸根离子连接形成三维网状结构。2个配合物中1,6-萘二磺酸根离子均没有与镍离子配位,只是起到平衡电荷的作用。室温下,配合物显示了较大的荧光发射峰,其最大发射峰分别在443和438nm。     

两个单核镍含氮配体配合物的合成、晶体结构及荧光性质(英文)

采用回流法在水溶剂中合成了2个含氮配体单核镍配合物[Ni(phen)2(H2O)2](1,6-nds)·2H2O(1)和[Ni(phen)3](1,6-nds)·10H2O(2)(1,6-nds=1,6-萘二磺酸根离子,phen=1,10-邻菲罗啉)。配合物1中,镍离子与2个1,10-邻菲罗啉和2个水分子配位,形成[Ni(phen)2(H2O)2]2+阳离子。2个没有配位的水分子通过氢键与[Ni(phen)2(H2O)2]2+和1,6-萘二磺酸根离子相互连接形成二维层状结构。配合物2中,镍离子与3个1,10-邻菲罗啉配位,形成[Ni(phen)3]2+阳离子。大量的氢键将自由的水分子和1,6-萘二磺酸根离子连接形成三维网状结构。2个配合物中1,6-萘二磺酸根离子均没有与镍离子配位,只是起到平衡电荷的作用。室温下,配合物显示了较大的荧光发射峰,其最大发射峰分别在443和438 nm。     

膦配体取代的乙基乙撑双铁配合物的合成、晶体结构及电化学催化性能

以母体配合物[Fe₂(CO)₆(μ-SCH₂CH (CH₂CH₃) S)](1)分别与三(2-呋喃基)膦、二苯基丙基膦、双(二苯基膦)乙炔、1,2-双(二苯基膦基)苯和脱羰试剂Me₃NO · 2H₂O反应,制备了单取代配合物[Fe₂(CO)₅(L)(μ-SCH₂CH (CH₂CH₃) S](L=P (2-C₄H₃O)₃,2;Ph₂PCH₂CH₂CH₃,3)、桥联配合物{[Fe₂(CO)₅(μ-SCH₂CH (CH₂CH₃) S)]₂(Ph₂PC≡CPPh₂)}(4)和螯合配合物[Fe₂(CO)₄(κ₂-(Ph₂P)₂(1,2-C₆H₄))(μ-SCH₂CH (CH₂CH₃) S)](5)。配合物2~5经元素分析、红外光谱、核磁共振氢谱和磷谱表征,并进一步得到单晶X射线衍射的确证。电化学研究表明,在弱酸HOAc作为质子源存在的情况下,这些配合物可以实现催化质子还原产生氢气的功能。     

膦配体取代的乙基乙撑双铁配合物的合成、晶体结构及电化学催化性能

以母体配合物[Fe₂(CO)₆(μ-SCH₂CH(CH₂CH₃)S)](1)分别与三(2-呋喃基)膦、二苯基丙基膦、双(二苯基膦)乙炔、1,2-双(二苯基膦基)苯和脱羰试剂Me₃NO·2H₂O反应,制备了单取代配合物[Fe₂(CO)₅(L)(μ-SCH₂CH(CH₂CH₃)S)](L=P(2-C₄H₃O)₃,2;Ph₂PCH₂CH₂CH₃,3)、桥联配合物{[Fe₂(CO)₅(μ-SCH₂CH(CH₂CH₃)S)]2(Ph₂PC≡CPPh₂)}(4)和螯合配合物[Fe₂(CO)₄(κ²-(Ph₂P)₂(1,2-C₆H₄))(μ-SCH₂CH(CH₂CH₃)S)](5)。配合物2~5经元素分析、红外光谱、核磁共振氢谱和磷谱表征,并进一步得到单晶X射线衍射的确证。电化学研究表明,在弱酸HOAc作为质子源存在的情况下,这些配合物可以实现催化质子还原产生氢气的功能。     

Synthesis and Crystal Structures of Tetraazamacrocycle NickelII Complexes Containing O-Phenylenedioxydithiophosphate Anion

Abstract

A tetraazamacrocycle nickel^II complex of O,O′-diaryldithiophosphate, [Ni(hmtade)] [S₂P(O₂C₆H₄-o)]₂ (1), and its unexpected complex methanolysis product, [Ni(hmtade)] [S₂P(OMe)(OC₆H₄(OH-o)]₂ (2) (the ligand hmtade is 5,7,7,12,14,14-hexamethyl-1,4,8,11- tetraazacyclotetradeca-1,11-diene), have been synthesized and characterized by elemental analysis, IR, ¹H(¹³C, ³¹P) NMR spectroscopies, thermogravimetric analysis, and single-crystal X-ray diffraction methods. The results show that the difference in O,O′-diaryldithiophosphate anions hardly brings about any influence on the structure of complex cation [Ni(hmtade)]²⁺. In the packing of 1, the molecules self-assemble into a folded two-dimensional (2D) network and which further links into a complicated 3D supramolecular framework. Two different kinds of 2D networks form independently via intermolecular hydrogen bonds and alternatively arrange into a novel 3D lamellar sandwich-layer structure in the packing of 2.     

芳基取代四甲基环戊二烯基铼羰基化合物的合成、晶体结构及催化性能

芳基取代的四甲基环戊二烯 C₅HMe₄Ar（Ar=Ph,4-CH₃Ph,4-OCH₃Ph,4-ClPh,4-BrPh） 分别与Re₂（CO）₁₀在二甲苯中加热回流,得到了5个单核配合物[（η⁵-C₅Me₄Ar）Re（CO）₃]（Ar=Ph （1）,4-CH₃Ph （2）,4-OCH₃Ph （3）,4-ClPh （4）,4-BrPh （5）]。通过元素分析、红外光谱、核磁共振氢谱对配合物1~5的结构进行了表征,用X射线单晶衍射法测定了配合物的结构。同时,研究了这五种配合物在芳香族化合物Friedel-Crafts烷基化反应中的催化活性。     

芳基取代四甲基环戊二烯基铼羰基化合物的合成、晶体结构及催化性能

芳基取代的四甲基环戊二烯 C₅HMe₄Ar（Ar=Ph,4-CH₃Ph,4-OCH₃Ph,4-ClPh,4-BrPh） 分别与Re₂（CO）₁₀在二甲苯中加热回流,得到了5个单核配合物[（η⁵-C₅Me₄Ar）Re（CO）₃]（Ar=Ph （1）,4-CH₃Ph （2）,4-OCH₃Ph （3）,4-ClPh （4）,4-BrPh （5））。通过元素分析、红外光谱、核磁共振氢谱对配合物1~5的结构进行了表征,用X射线单晶衍射法测定了配合物的结构。同时,研究了这五种配合物在芳香族化合物Friedel-Crafts烷基化反应中的催化活性。     

Syntheses and Characterization of Two Diiron Dithiolate Complexes with Electron-withdrawing and Electron-donating Substitution

Two diiron dithiolate complexes [Fe_2(CO)_6(1,8-S_2-2-CH_2OOCPhC_(10)H_5)] 1 and[Fe_2(CO)_6(1,8-S_2-2-CH_2OOCPh-4-NO_2C_(10)H_5)]2 were synthesized in high yield. The complexes have been confirmed by single-crystal X-ray diffraction and characterized by IR, UV-Vis, ~1H NMR spectroscopy and cyclic voltammetry. They contain a butterfly Fe_2S_2 core with the Fe1–Fe_2 distances of 2.5237(7) ? in 1 and 2.5125(12) ? in 2, falling in the normal range of Fe–Fe bond length(2.49 ~ 2.57 ?). The cyclic voltammetry has been used to investigate the electrochemical properties and the electrocatalytic proton reduction for 1 and 2. The complexes display reduction peaks at –1.074 V, –1.535 V(1) and –0.869 V, –1.247 V(2) vs. Fc/Fc+, respectively. With using p-Ts OH acid of different concentration, the reduction peak of complex 2 grows non-linear; on the contrary, that of complex 1 is linear with the addition of the acid. Cyclic voltammetry revealed the two complexes are good catalysts in the CH_3CN/NBu_4PF_6 solution.     

Mechanism of Diiron Hydrogenase Complexes Controlled by Nature of Bridging Dithiolate Ligand

Bio-inorganic complexes inspired by hydrogenase enzymes are designed to catalyze the hydrogen evolution reaction (HER). A series of new diiron hydrogenase mimic complexes with one or two terminal tris(4-methoxyphenyl)phosphine and different μ-bridging dithiolate ligands and show catalytic activity towards electrochemical proton reduction in the presence of weak and strong acids. A series of propane- and benzene-dithiolato-bridged complexes was synthesized, crystallized, and characterized by various spectroscopic techniques and quantum chemical calculations. Their electrochemical properties as well as the detailed reaction mechanisms of the HER are elucidated by density functional theory (DFT) methods. The nature of the μ-bridging dithiolate is critically controlling the reaction and performance of the HER of the complexes. In contrast, terminal phosphine ligands have no significant effects on redox activities and mechanism. Mono- or di-substituted propane-dithiolate complexes afford a sequential reduction (electrochemical; E) and protonation (chemical; C) mechanism (ECEC), while the μ-benzene dithiolate complexes follow a different reaction mechanism and are more efficient HER catalysts.     

Investigations on the Synthesis,Structural Characterization,and Crystal Structures of Three Diiron and Tetrairon Azadithiolate Complexes

Three diiron and tetrairon azadithiolate complexes as models for the active site of [FeFe] hydrogenase were prepared. Reaction of complex Fe₂(SCH₂OH)₂(CO)₆ and NH₂CH₂CH₂CH₂OCH₃ resulted in the diiron azadithiolate hexcarbonyl complex Fe₂[(SCH₂)₂NCH₂CH₂CH₂OCH₃](CO)₆ ( 1 ) in moderate yield. Furthermore, treatment of complex 1 with mono phosphine ligand PPh₃ and diphosphine ligand Ph₂PCH₂CH₂PPh₂ in the presence of decarbonylation reagent Me₃NO · 2H₂O yielded the phosphine‐substituted azadithiolate complexes Fe₂[(SCH₂)₂NCH₂CH₂CH₂OCH₃]CO)₅(PPh₃) ( 2 ) and {Fe₂[(SCH₂)₂NCH₂CH₂CH₂OCH₃](CO)₅}₂(Ph₂PCH₂CH₂PPh₂) ( 3 ) respectively. The new complexes 1 – 3 were fully characterized by elemental analysis, IR, ¹H, ¹³C, ³¹P NMR spectroscopy and X‐ray crystallography. It is worthy to note that the crystallographic studies show the unusual difference of the methoxypropanyl substituent on the N atom of complexes 1 and 2 , largely because of the affection of phosphine ligand PPh₃. In addition, complex 1 was found to be a catalyst for H₂ production under electrochemical condition.     

两个双核铁（Ⅲ）和三足配体的配合物的合成和晶体结构

运用三足四齿配体三（2－甲基吡啶）胺（TPA）或三（2－甲基苯丙咪唑）胺（TBA）,得到两个双核铁(III)配合物，[Fe₂L₂(μ₂-O)(μ₂-p-NH₂-C₆H₄COO)]³⁺ (L = TPA, 1 和 L = TBA, 2)。两个配合物均为单斜晶系，空间群为P2(1)/c.晶胞参数 1: a = 1.4529(4), b = 1.6622(5), c = 2.0625(6) nm, β= 100.327(5)º, V = 4.900(3) nm³, z = 4, F(000) = 2344, 分子量M_r = 1142.91, Dc = 1.549 g/cm³, R₁ = 0.0544, R₂ = 0.0962. 2: a = 1.3378(4), b = 2.1174(7), c = 2.4351(7) nm, β= 97.315(6)º, V = 6.842(4) nm³, z = 4, F (000) = 3116, 分子量M_r = 1505.08, Dc = 1.444 g/cm³, R₁ = 0.0793, R₂ = 0.1623. 在两个双核铁(III)配合物中，中心的三价铁和配体TPA或TBA上的四个氮原子和两个氧原子通过不同的桥形成一个畸变的八面体构型。     

含叠氮酸根的锰(Ⅱ)配合物的合成与晶体结构

Two new mononuclear Mn(Ⅱ) complexes Mn(phen)₂(N₃)₂ (1) and [Mn(phen)₂(N₃)(H₂O)]ClO₄·H₂O (2) have been synthesized and structurally characterized, where phen is 1,10-phenanthroline. Complex 1 crystallizes in the P1 space group, with lattice parameters a=8.1688(2)?, b=11.1218(2)?, c=12.6881(2)?, α=83.558(3)°, β=82.287(3)°, γ=73.643(3)°, V=1092.7(4)?³, D_c=1.518Mg·m^-3, Z=2, F(000)=510, R₁=0.0620, wR₂=0.0958 (based on F²), S=0.981. Complex 2 crystallizes in the P1 space group, with lattice parameters a=8.6543(2)?, b=8.9767(2)?, c=17.5915(4)?, α= 93.399(3)°, β=102.806(3)°, γ=106.234(3)°, V=1268.7(4)?³, D_c=1.552Mg·m^-3, Z=2, F(000)=606, R₁=0.0672, wR₂=0.1781 (based on F²), S=1.047. In complex 1, the Mn atom is coordinated by six nitrogen atoms of two phen molecules and two N₃^- ions with the Mn-N distances ranging from 2.142(4) to 2.318(4)?. The coordinated phen molecules of the adjacent Mn(phen)₂(N₃)₂ moieties experience π-π stacking which is responsible for the crystal packing. In complex 2, the Mn atom is coordinated by five nitrogen atoms of two phen molecules and one N₃^- ion with the Mn-N distances ranging from 2.152(5) to 2.291(5)?. The approximately octahedral environment was completed by the oxygen atom of the coordinated water molecule with the Mn-O distance of 2.180(5)?. The hydrate water molecule is hydrogen-bonded to one of the O atoms of free ClO₄^- anion. ?     

烃基取代茚基钌羰基化合物的合成及晶体结构(英文)

配体C9H7R(R=CH2CH2CH3(1),CH(CH3)2(2),C5H9(3),CH2C6H5(4),CH2CH=CH2(5))分别与Ru3(CO)12在二甲苯或庚烷中加热回流,得到了6个双核配合物[(η5-C9H6R)Ru(CO)(μ-CO)]2(R=CH2CH2CH3(6),CH(CH3)2(7),C5H9(8),CH2C6H5(9),CH2CH=CH2(10))和[(η5-C9H6)(H3CH2C)CHCH(CH2CH3)(η5-C9H6)][Ru(CO)(μ-CO)]2(11)。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,9,10和11的结构。     

烃基取代茚基钌羰基化合物的合成及晶体结构

配体C₉H₇R(R=CH₂CH₂CH₃ (1),CH₂(CH₃)₂ (2),C₅H₉ (3),CH₂C₆H₅ (4),CH₂CH=CH₂ (5))分别与Ru₃(CO)12在二甲苯或庚烷中加热回流,得到了6个双核配合物[(η⁵-C₉H₆R)Ru(CO)(μ-CO)]₂(R=CH₂CH₂CH₃ (6),CH₂(CH₃)₂ (7),C₅H₈ (8),CH₂C₆H₅ (9),CH₂CH=CH₂ (10))和[(η⁵-C₉H₆)(H₃CH₂C)CHCH(CH₂CH₃)(η⁵-C₉H₆)] [Ru(CO)(μ-CO)]₂ (11).通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,9,10和11的结构.     

含乙酰氧肟酸配体的席夫碱钒配合物的合成、结构及其抑制幽门螺旋杆菌脲酶研究(英文)

本文合成了2个新的含乙酰氧肟酸配体的席夫碱钒配合物,[VⅢL1(HAHA)](1)和[VⅤOL2(AHA)](2),其中L1为N,N′-二(5-甲基水杨基)乙烷-1,2-二胺的二价阴离子,L2为2-{[2-(2-羟乙基氨基)乙亚胺基]甲基}-6-甲基苯酚的一价阴离子,HAHA和AHA分别为乙酰氧肟酸的一价和二价阴离子,通过物理-化学方法以及单晶X-射线衍射表征了它们的结构。在每个化合物中,V原子都采取八面体配位构型。本文还研究了配合物的热稳定性以及其对幽门螺旋杆菌脲酶的抑制活性。在浓度为100μmol·L-1时,配合物1和2对脲酶的抑制率分别为37.2%和81.5%,其中配合物2的IC50值为21.5μmol·L-1。分子对接研究表明配合物2与脲酶活性中心存在有效的作用力。     

Synthesis,Characterization, and Crystal Structure of Tertiary Phosphine-Substituted Diiron Propanedithiolate Complexes

As the active site models of [FeFe]-hydrogenase, two new tertiary phosphine-substituted diiron propanedithiolate complexes [(μ-PDT)Fe₂(CO)₅L] (PDT = SCH₂CH₂CH₂S, L = P(PhMe-m)₃, 1; PPh₂(CH₂CH₂CH₃), 2) have been prepared through carbonyl substitution reactions of parent complex [(μ-PDT)Fe₂(CO)₆] (A) with P(PhMe-m)₃ or PPh₂(CH₂CH₂CH₃) in the presence of the decarbonylating agent Me₃NO·2H₂O in MeCN at room temperature. The new complexes 1 and 2 were fully characterized by elemental analysis, FT-IR, ¹H, ¹³C{¹H}, and ³¹P{¹H} NMR spectroscopy, as well as for 1 by X-ray crystallography. In addition, the crystal structure of 1 has indicated that the phosphorus atom of the P(PhMe-m)₃ ligand resides in an apical position of the pseudo-square-pyramidal geometry of the tertiary phosphine-coordinated Fe₂ atom.