基于1-(2-吡啶甲基)-1, 2, 4-三唑的金属有机化合物的合成及反应研究

本文合成了1-（2-吡啶甲基）-1,2,4-三唑（L）,并研究了其与有机锡和羰基钼（钨）的配位反应,合成了通过三唑4位氮原子以单齿形式配位的有机锡衍生物L₂SnR₂Cl₂（R=Me,n-Bu或Ph）和羰基金属配合物LM（CO）₅（M=Mo或W）,以及N,N螯合双齿配位的四羰基金属配合物LM（CO）₄。当用氯化苄处理L时,制得了相应的三唑盐,该盐用氧化银处理后与M（CO）₅THF或M（CO）₄（NHC₅H₁₀）₂（NHC₅H₁₀为哌啶）反应,得到了基于三唑的氮杂环卡宾衍生物L’M（CO）₅和L’M（CO）₄（L’=1-（2-吡啶甲基）-4-苄基-1,2,4-三唑-5-碳烯）。X-射线单晶衍射分析表明,在L’M（CO）₅中氮杂环卡宾配体L’表现为通过卡宾碳配位的单齿配体;而在L’M（CO）₄中,L’表现为通过卡宾碳和吡啶氮原子配位的螯合[C,N]双齿配体。     

桥头碳上氮杂芳基功能化的双吡唑甲烷与羰基钨反应

研究了(氮甲基咪唑-2-基)双(3,5-二甲基吡唑)甲烷(L1),2-吡啶基双(3,5-二甲基吡唑)甲烷(L2)及4-吡啶基双(3,5-二甲基吡唑)甲烷(L3)与羰基钨的反应,合成了一系列以单齿,双齿及三齿氮配位的羰基金属衍生物LW(CO)5(L=L1或L3),LW(CO)4(L=L1,L2或L3)和LW(CO)3(L=L1或L2)。核磁,红外及X-射线单晶衍射分析表明这3种配体表现出了可变的配位方式。在LW(CO)5中,当配体为L1时,其倾向于通过咪唑氮与金属配位,而为L3则倾向于利用吡啶氮与金属作用;在LW(CO)4中,配体L1表现为通过咪唑氮和吡唑氮原子配位的[N,N′]双齿配体,而L2和L3表现为通过吡唑氮原子配位的[N,N]双齿配体;在LW(CO)3中,L1和L2起着[N,N,N′]三齿螯合配体的作用。     

基于3,5-二(3-吡啶)-4-氨基-1,2,4-三唑配体的Co(Ⅱ)和Cu(Ⅱ)配合物的合成与晶体结构（英文）

利用3,5-二(3-吡啶)-4-氨基-1,2,4-三唑(L)配体与Co(Ⅱ)/Cu(Ⅱ)盐室温下反应得到了一维的配位聚合物{[CoL(H_2O)_4]SO_4·H_2O}n(1)和单核配合物[Cu(hfac)2L2](2,hfac=hexafluoroacetylacetonate)。通过红外、元素分析及X射线单晶衍射等检测手段对所合成的配合物进行了表征。结构研究表明,配合物1中,配体L呈顺式构型,采取双齿配位方式桥联Co(Ⅱ)离子形成一维正弦链状结构,一维链通过多种氢键相互作用连接进一步形成三维网状结构;溶剂水分子和硫酸根阴离子通过氢键连接在框架上。配合物2中,配体L则采取单齿配位方式,与Cu(Ⅱ)离子形成离散型的单核结构,通过多重氢键作用进而连接成三维网状结构。     

桥头碳上氮杂芳基功能化的双吡唑甲烷与羰基钨反应（英文）

研究了(氮甲基咪唑-2-基)双(3,5-二甲基吡唑)甲烷(L1),2-吡啶基双(3,5-二甲基吡唑)甲烷(L2)及4-吡啶基双(3,5-二甲基吡唑)甲烷(L3)与羰基钨的反应,合成了一系列以单齿,双齿及三齿氮配位的羰基金属衍生物LW(CO)5(L=L1或L3),LW(CO)4(L=L1,L2或L3)和LW(CO)3(L=L1或L2)。核磁,红外及X-射线单晶衍射分析表明这3种配体表现出了可变的配位方式。在LW(CO)5中,当配体为L1时,其倾向于通过咪唑氮与金属配位,而为L3则倾向于利用吡啶氮与金属作用;在LW(CO)4中,配体L1表现为通过咪唑氮和吡唑氮原子配位的[N,N′]双齿配体,而L2和L3表现为通过吡唑氮原子配位的[N,N]双齿配体;在LW(CO)3中,L1和L2起着[N,N,N′]三齿螯合配体的作用。     

镍(Ⅱ)基双氮杂环卡宾配合物的合成及其晶体结构

以咪唑和取代氯化苄为原料,经氮烷基化反应合成三个氮杂环卡宾(NHC)配体[L1:N,N-二苄基咪唑-2-亚基,L2:N,N-二(4-甲基苄基)咪唑-2-亚基,L3:N,N-二(4-氯苄基)咪唑-2-亚基];再以咪唑官能团化的N-杂环卡宾配体和氯化镍为原料,通过金属交换反应合成三个新型的镍基双氮杂环卡宾配合物[Ni(NHC)_2]Cl_2(C1~C3),其结构经~1H NMR,IR,元素分析和X-单晶射线衍射表征。配合物C1和C3属于单斜晶系,分别为P2_1/n和P2_1/c空间群。配合物C2属于三斜晶系,为P1空间群。C1~C3的CCDC分别为:1433176,1433177和1433179。     

吡啶氮桥联三唑卡宾反应性质及其Pd(Ⅱ)-配合物催化杂芳环与芳基溴的α-烷基化反应研究

报道了吡啶氮桥联的双环三唑鎓盐1在NaH,K2CO3为碱的条件下脱去质子,分别形成三唑卡宾2和吡啶氮桥联三唑卡宾二聚体4,研究了2和4与亲电试剂的反应性质,2与水的反应产物Ⅳ-乙基-N'-吡啶基甲醛肼3经单晶衍射结构分析.考察了配体1的卡宾-Pd(Ⅱ)配合物催化咖啡因与芳基溴的α-芳基化反应,在优化催化反应条件下,比较了不同三唑鎓盐之间的催化活性.结果表明,三唑鎓盐1表现出优良的催化活性.     

均苯四酸辅助的异构化二吡啶基三唑钴配合物的合成、表征及其对高氯酸铵的催化分解

在水热条件下,以辅助配体均苯四酸,合成了3个二吡啶基三唑钴（Ⅱ）配位化合物,[Co（3,3′-Hbpt）2（H2pm）（H20）2]·2H20（1）,[Co（4,4′Hbpt）（pm）o．5（H20）]。3H20（2）和[Co（3,4′Hbpt）（pm）05（H20）3]′2H20（3）（其中3,3′-Hbpt为3,5-二（3．吡啶）-1氢-1,2,4-三唑,4,4′-bpt为3,5-二（4-吡啶）-1氢-1,2,4-三唑,3,4′-Hbpt为3-（3-吡啶）-5-（4′-吡啶）-1氢-1,2,4-三唑,H4pm为均苯四酸）．通过元素分析、红外、热重以及单晶X射线衍射等技术手段对化合物进行了表征．结构分析表明,在化合物1中,H2pm^2-以双单齿模式桥连相邻的金属离子形成一维的链,链与链之间进而通过3,3′-Hbpt与羧酸基团构成的O-H…N氢键作用形成了一个二维层状结构;化合物2呈现出具一维通道的三维结构,其中,pm^4-以单齿和双单齿配位模式与钴离子配位形成二维网格结构,相邻的层之间再通过Hbpt连接形成三维的开放式结构;在化合物3中,钴离子与3,4′-Hbpt中的吡啶氮原子形成螺旋链,pm^4-则进一步以双单齿桥连模式将相邻的螺旋链连接成一个二维结构．借助DSC技术探究了化合物1-3对高氯酸铵的热分解效应,结果发现,添加化合物1和2之后高氯酸铵热分解速率明显加快,放热量大为增加,有望成为新型含能燃烧催化剂．     

由2-(4'-羧基苯基)咪唑-4,5-二羧酸构筑的过渡金属配位聚合物的合成、结构及性质

在溶剂热条件下,由2-(4′-羧基苯基)咪唑-4,5-二羧酸(H_4L,C_(12)H_8N_2O_6),合成了4个配位聚合物{[M(H_3L)_2]·2H_2O}_n(M=Zn(1),Cd(2),Co(3)),[Cd(H_2L)(H_2O)]_n(4)。用元素分析、红外光谱、热重分析和单晶X射线衍射对配合物进行了表征和结构分析。结构分析结果表明:1～3是异质同晶。配体失去1个质子以H_3L~-的形式通过单齿和N,O-双齿螯合的配位模式与中心金属离子配位,构成一个略有变形的八面体结构。对于配合物4来说,配体失去2个质子以H_2L~(2-)的形式分别通过单齿和N,O-双齿螯合的配位方式与Cd~(2+)配位,中心离子采取扭曲的七配位五角双锥配位模式,并且通过配体苯环上羧基氧原子的双齿桥联作用连接2个中心离子,形成四元环的双核结构;同时呈现双节点(3,6)-连接的二维拓扑网络(4.4.4)(4.4.4.4.4.4.5.6.6.6.6.6)。测定了产物的固体荧光光谱;用EtBr荧光探针法研究了配体及配合物与ct-DNA的相互作用。     

以2-(1-吡唑基甲基)吡啶类化合物为配体的羰基钼、钨衍生物的合成及结构

合成了2-[1-(3-叔丁基)吡唑基甲基]吡啶(CH2(Py)(3-ButPz)),并研究了羰基钼(钨)与该配体及其类似物2-(1-吡唑基甲基)吡啶(CH2(Py)(Pz))和2-[1-(3,5-二甲基)吡唑基甲基]吡啶(CH2(Py)(3,5-Me2Pz))的反应,合成了6个含双齿螯合的2-(1-吡唑基甲基)吡啶类配体的四羰基金属衍生物CH2(Py)(3-ButPz)M(CO)4,CH2(Py)(Pz)M(CO)4和CH2(Py)(3,5-Me2Pz)M(CO)4(M=Mo或W)。当用SnCl4处理CH2(Py)(3,5-Me2Pz)M(CO)4时,Sn-Cl键对金属中心发生氧化加成得到2个杂双核金属有机化合物CH2(Py)(3,5-Me2Pz)M(CO)3(Cl)SnCl3。所有新化合物均通过了红外和核磁的表征,CH2(Py)(3-ButPz)W(CO)4和CH2(Py)(3,5-Me2Pz)W(CO)3(Cl)SnCl3的结构还得到了X-射线单晶衍射的确证。用循环伏安法测定了四羰基金属衍生物的电化学性质。     

有机锡2-[(1,2,4-三唑-1-基)甲基硫代]苯甲酸酯的合成与生物活性

通过硫代水杨酸与(1-氯甲基)-1,2,4-三唑盐酸盐在碱性条件下的反应, 合成了2-[(1,2,4-三唑-1-基)甲基硫代]苯甲酸. 利用该酸与(R₃Sn)₂O(R=Et, n-Bu, Ph), Cy₃SnOH(Cy为环己基)或Et₂SnO反应, 得到了5个有机锡羧酸酯. 用X射线单晶衍射测定了三正丁基锡2-[(1,2,4-三唑-1-基)甲基硫代]苯甲酸酯的晶体结构. 在该化合物中, 锡为五配位的三角双锥结构. 该化合物通过三唑四位氮原子与锡配位, 形成一维链状配位高分子. 初步的生物活性测试结果表明, 所有的有机锡化合物都表现出了明显的抗真菌活性.     

Reaction of metal carbonyls with 2-hydroxy-1-naphthaldeyde methanesulfonylhydrazone and characterization of the substitution products

Five new complexes, [M(CO)₅(nafmsh)] [M?=?Cr, 1; Mo, 2; W, 3], [Re(CO)₄Br(nafmsh)], 4 and [Mn(CO)₃(nafmsh)], 5 have been synthesized by the photochemical reaction of metal carbonyls [M(CO)₆] (M?=?Cr, Mo, W), [Re(CO)₅Br], and [Mn(CO)₃Cp] with 2-hydroxy-1-naphthaldehyde methanesulfonylhydrazone (nafmsh). The complexes have been characterized by elemental analysis, EI mass spectrometry, FT-IR, and ¹H NMR spectroscopy. The spectroscopic studies show nafmsh is a monodentate ligand coordinating via the imine N donor atom in 1–4 and as a tridentate ligand in 5.     

Photochemical reactions of group VIB metal carbonyls with heterocyclic Schiff bases derived from 4-amino -3-hydrazino-5-mercapto-1,2,4-triazole

The new complexes, M(CO)₅(Schiff base) [M?=?Cr; 1, Mo; 2, W; 3, Schiff base?=?4-salicylidenamino-3-hydrazino-5-mercapto-1,2,4-triazole, SAHMT, a; 4-(2-hydroxynaphthylidenamino)-3-hydrazino-5-mercapto-1,2,4-triazole, 2HNAHMT, b; 4-(3-hydroxybenzylidenamino)-3-hydrazino-5-mercapto-1,2,4- triazole, 3HBAHMT, c; 4-(4-hydroxybenzylidenamino)-3-hydrazino-5-mercapto-1,2,4- triazole, 4HBAHMT, d; 4-(5-bromosalicylidenamino)-3-hydrazino-5-mercapto-1,2,4-triazole, 5BrSAHMT, e; were synthesized by photochemical reaction of metal carbonyls M(CO)₆ (M?=?Cr, Mo, W) with new heterocyclic Schiff bases derived from 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole, a–e. The ligands and complexes have been characterized by elemental analysis, EI-mass spectrometry, FT-IR, ¹H and ¹³C-{¹H}-NMR spectroscopy. The spectroscopic studies show that Schiff bases, a–e, are monodentate and coordinate via azomethine N donor to the central metal atom in M(CO)₅(Schiff base) (M?=?Cr, Mo, W).     

Theoretical insights into the relative bonding of normal and abnormal N‐heterocyclic carbenes in [PdCl2(NHCR)2] and [PdCl2(NHCR)(aNHCR)] (R = H,Ph, Mes)

Quantum chemical insights into normal Pd‐C2(NHC^R) and abnormal Pd‐C5(aNHC^R) bonding, dominated by dispersion interactions in N‐hetereocyclic carbene complexes [PdCl₂(NHC^R)₂] ( I , R = H; II , R = Ph; III , R = Mes (2,4,6‐trimethyl)phenyl)) and [PdCl₂(NHC^R)(aNHC^R] ( IV , R = H; V , R = Ph; VI , R = Mes) have been investigated at DFT and DFT‐D3(BJ) level of theory with particular emphasis on the effects of the noncovalent interactions on the structures and the nature of Pd‐C2(NHC^R) and Pd‐C5(aNHC^R) bonds. The optimized geometries are good agreement with the experimental values. The Pd‐C bonds are essentially single bond. Hirshfeld charge distributions indicate that the abnormal aNHC^R carbene ligand is relatively better electron donor than the normal NHC^R carbene ligand. The C2 atom has larger %s contribution along Pd‐C2 bond than the C5 atom along Pd‐C5 bond. As a consequence the Pd‐C2(NHC^R) bonds are relative stronger than the Pd‐C5(aNHC^R) bonds. Thus, the results of natural hybrid orbital analysis support the key point of the present study. Calculations predict that for bulky substituent (R = Ph, Mes) at carbene, the Pd‐C2(NHC^R) bond is stronger than Pd‐C5(aNHC^R) bond due to large dispersion energy in [PdCl₂(NHC^R)₂] than in [PdCl₂(NHC^R)(aNHC^R)]. However, in case of non‐bulky substituent with small and almost equal contribution of dispersion energy, the Pd‐C2(NHC^R) bond is relative weaker than Pd‐C5(aNHC^R) bond. The bond dissociation energies are dependent on the R substituent, the DFT functional and the inclusion of dispersion interactions. Major point of this study is that the abnormal aNHCs are not always strongly bonded with metal center than the normal NHCs. Effects of dispersion interaction of substituent at nitrogen atoms of carbene ligand are found to play a crucial role on estimation of relative bonding strengths of the normal and abnormal aNHCs with metal center. © 2016 Wiley Periodicals, Inc.     

Photochemical reactions of <Emphasis Type="Italic">cis</Emphasis>-[(η<Superscript>4</Superscript>-NBD)M(CO)<Subscript>4</Subscript>] (NBD = norbornadiene; M = Cr,Mo) olefin complex with ligand,containing S and N donor atoms

New complexes cis-[M(CO)₄-DABRd] (M = Cr(I), Mo(II) and fac-[M(CO)₃-SAT] (M = Cr(III), Mo(IV)) have been synthesized by the photochemical reactions of cis-[(η⁴-NBD)M(CO)₄] (NBD is norbornadiene; M=Cr, Mo) with 5-(4-dimethylaminobenzylidene) rhodanine (DABRd) and salicylidene-3-amino-1,2,4-triazole (SAT) ligands and characterized by elemental analysis, FT-IR and ¹H NMR spectroscopy, and mass spectrometry. The spectroscopic studies show that the DABRd ligand acts as a bidentate ligand coordinating via both NH-(S)C=S sulfur donor atoms in I and II and SAT ligand behaves as a tridentate ligand coordinating via its all imine nitrogen-C=N-donor atoms in III and IV to the metal center. The article was submitted by the authors in English.     

Dinuclear amine-thiophenolate complexes coligated by ferrocenemonocarboxylate and 1,1'-ferrocenedicarboxylate anions: preparation, characterization and structures of trinuclear [LMII 2(O2CC5H4FeCp)]+ and Pentanuclear [(LMII 2)2(O2CC5H4)2Fe]2+ complexes (M=Co, Ni, Zn)

A series of novel tri- and pentanuclear complexes composed of dinuclear LM(2) units (M=Co, Ni, Zn; L=24-membered macrocyclic hexaazadithiophenolate ligand) and ferrocenecarboxylate ([CpFeC(5)H(4)CO(2)](-)) or 1,1'-ferrocenedicarboxylate ([Fe(C(5)H(4)CO(2))(2)](2-)) groups is reported. The complexes [LM(II) (2)(O(2)CC(5)H(4)FeCp)](+) (M=Co (6), Ni (7), Zn (8)) and [(LM(II) (2))(2)(O(2)CC(5)H(4))(2)Fe](2+) (M=Co (9), Ni (10)) have been prepared by substitution reactions from labile [LM(II) (2)L'](+) precursors (L'=Cl, OAc) and the respective ferrocenecarboxylate anions in methanol. Mixed-valent [(LCo(II)Co(III))(2)(O(2)CC(5)H(4))(2)Fe](4+) (11) was prepared by oxidation of 9 with bromine. Complexes 7[BPh(4)], 8[BPh(4)], 9[BPh(4)](2), 10[BPh(4)](2), and 11[ClO(4)](4) have been characterized by X-ray crystallography; showing that the ferrocenyl carboxylates act as bidentate (7, 8) or bis-bidentate (9-11) bridging ligands towards one or two bioctahedral LM(2) subunits, respectively. The structures are retained in solution as indicated by NMR spectroscopic studies on the diamagnetic Zn(2)Fe complex 8[ClO(4)]. Electrochemical studies reveal significant anodic potential shifts for the oxidation potential of the ferrocenyl moieties upon complexation and the magnitude of the potential shift appears to correlate with the charge of the LM(2) subunits. This is qualitatively explained in terms of destabilizing electrostatic (Coulomb) interactions between the M(2+) ions of the LM(2) unit and the proximate ferrocenium fragment. An analysis of the temperature-dependent magnetic susceptibility data for 10[BPh(4)](2) shows the presence of weak ferromagnetic magnetic exchange interactions between the Ni(II) ions in the LNi(2) units. The exchange coupling across the ferrocenedicarboxylate bridge is negligible.     

Sulfur-containing carbene-metal compounds: General route from carbon disulfide manganese complexes; X-ray structure of 1,3-dithiol-2-ylidenemanganese(I) derivative

Chiral carbene-manganese(I) complexes have been synthesized by the cyclo-addition of dimethyl acetylenedicarboxylate to the coordinated CS₂ ligand in Mn(η²-CS₂)(CO)(L)C₅H₄R (L = P(OMe)₃; PMe₂Ph; PMe₃). Irrespective of the nature of the ligand L, these 1,3-dithiol-2-ylidenemanganese(I) complexes are stable towards isomerisation into heterometallocycles and exhibit low frequency carbonyl absorption bands in the infrared consistent with a strong electron releasing effect of the carbene ligand. The structure of Mn(CS₂C₂(CO₂Me)₂)(CO)(P(OMe)₃)(C₅H₅) has been determined by X-ray analysis of a suitable crystal. The molecule shows a carbene carbonmanganese bond C(7)Mn of length 1.876 Å and a planar carbene which does not adopt the 1,3-dithiolium aromatic-ring geometry but contains a carboncarbon double bond, C(8)C(9), of length of 1.341 Å. The CO₂Me groups are out of the plane of the carbene ligand and two positions with equal occupancy are found for each oxygen atom O(3) and O(5) belonging to the CO groups.     

Syntheses,crystal structures,and fluorescent properties of two 2-D Cd(II) complexes based on 2-((1H-1,2,4-triazol-1-yl)methyl)-1H-benzimidazole and 1,2,4,5-benzenetetracarboxylate

Two complexes formulated as {[Cd(btec)_0.5(tmb)H₂O]·4H₂O}_n (1) and {[Cd(H₂btec)(tmb)(H₂O)]·2H₂O}_n (2) (H₄btec?=?1,2,4,5-benzenetetracarboxylic acid, tmb?=?2-((1H-1,2,4-triazol-1-yl)methyl)-1H-benzimidazole) have been synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. Single crystal X-ray diffraction shows that 1 has a 2-D layer structure in which tmb bridges and all of the carboxylates from 1,2,4,5-benzenetetracarboxylate chelate. In 2 Cd(II) ions are bridged by monodentate carboxylates leading to a 2-D layer structure with all tmb ligands coordinated monodentate to Cd(II), hanging at two sides of the layers. Complexes 1 and 2 are further extended to 3-D supramolecular structures by hydrogen bonding interactions. Luminescent properties have been investigated in the solid state at room temperature.     

微波辐射下合成5-(2-甲基/三氟甲基-苯并咪唑-1-亚甲基)-3-(苯基/p-取代苯基)-2H-1',2',4'-三唑[3,4-b]-1

分别采用微波辐射法和加热回流的常规方法, 将1-氨基-2-(2-甲基/三氟甲基-苯并咪唑-1-亚甲基)-5-巯基-1,3,4-三唑与α-溴代芳基乙酮3a～3e反应, 合成了一系列未见文献报道的1,2,4-三唑[3,4-b]-1',3',4'-噻二嗪类化合物4a～4e 和5a～5e. 微波辐射法具有反应时间短、产率高、副反应少等优点. 标题化合物经元素分析, IR, ¹H NMR, MS确证结构.     

Chrom-, molybdän-, wolfram- und mangan-komplexe von 1-phenyl-4,5-dihydroborepin

1-Phenyl-4,5-dihydroborepin (I) reacts with suitably substituted carbonyls of Cr, Mo, and W to yield stable complexes LM(CO)₄ with L = I and M = Cr, Mo, W. Irradiation of (C₅H₅)Mn(CO)₃ in the presence of I produces labile (C₅H₅)MnL(CO). Large upfield ¹¹B NMR shifts in these complexes with respect to I indicate that the born atom participates in the metalligand bonding.