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(英文)

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。     

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

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（H₂O）₄]SO₄·H₂O}_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。     

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

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（H₂O）₄]SO₄·H₂O}_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

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.     

3-甲基-4-乙基-5-[2(或4)-吡啶基]-1，2，4-三唑银(Ⅰ)配合物的合成、晶体结构和光学性质

以3-甲基-4-乙基-5-（2-吡啶基）-1,2,4-三唑（L）和3-甲基-4-乙基-5-（4-吡啶基）-1,2,4-三唑（L''）为配体分别合成了2个银(Ⅰ)配合物[Ag2（μ-L）₂L₂（NO₃）₂]（1）和{[Ag₂（μ-L''）₂（H₂O）₂]（NO₃）₂}_n（2）,测定了X射线单晶结构,用红外光谱、荧光和热重等进行了表征。2个配合物都属于三斜晶系,空间群为P1。晶体结构分析表明2个配合物都具有畸变的四面体结构[AgN₃O]。配合物1.是一个双核银(Ⅰ)配合物,NO₃^-参与配位;而配合物2是一个配位聚合物,水分子参与配位。     

N, N’-双(3-吡啶醛)-(1R, 2R)-环己二胺席夫碱Ag(Ⅰ)配合物的合成、结构和荧光性质研究

以3-吡啶醛和（1R,2R）-环己二胺进行缩合得到Schiff碱配体L¹,然后,用配体L¹和AgNO₃进行配位反应,得到配合物[Ag（L¹）（NO₃）]_n（1）,并用元素分析、FT-IR、X-射线单晶衍射、热重分析、粉末衍射对其进行了表征。晶体结构表明：配合物1属于单斜晶系,C2空间群,Ag（Ⅰ）的配位环境均为扭曲四面体,分别和硝酸根的氧原子,配体中的2个吡啶氮原子以及1个亚胺氮原子配位,配体L¹有2种配位模式,其中,1个配体用两臂的2个吡啶氮原子分别和2个Ag（Ⅰ）离子配位,另外1个配体用两臂的2个吡啶氮原子分别和2个Ag（Ⅰ）离子配位,同时2个亚胺氮原子也分别和2个Ag（Ⅰ）离子配位,这样配合物形成3D孔状结构。同时研究了配合物的固体荧光性质。     

手性配体2, 5-二(4, 5-蒎烯-2-吡啶)吡嗪及其铼配合物的合成与表征

本文报道了手性配体2, 5-二(4, 5-蒎烯-2-吡啶)吡嗪(L)及其铼配合物[Re(CO)₃Cl(L)] ·DMF的合成与表征。X射线单晶衍射分析表明配体L晶体为单斜P2₁空间群, 而配合物[Re(CO)₃Cl(L)] ·DMF晶体为正交P2₁2₁2₁空间群。配合物[Re(CO)₃Cl(L)] ·DMF中铼原子与配体中的2个氮原子、3个羰基中的碳原子以及1个氯原子配位。CD谱和VCD谱测试表明, 配体和配合物都表现出光学活性。受光激发时, 配体和配合物分别在420和650 nm处发光。配体和配合物都具有二阶非线性光学性质, 其二阶非线性光学效应分别为尿素的0.4和0.3倍。     

3-甲基-4-乙基-5-[2(或4)-吡啶基]-1,2,4-三唑银(Ⅰ)配合物的合成、晶体结构和光学性质

以3-甲基-4-乙基-5-（2-吡啶基）-1,2,4-三唑（L）和3-甲基-4-乙基-5-（4-吡啶基）-1,2,4-三唑（L''）为配体分别合成了2个银（Ⅰ）配合物[Ag₂（μ-L）₂L₂（NO₃）₂]（1）和{[Ag₂（μ-L''）₂（H₂O）₂]（NO₃）₂}_n（2）,测定了X射线单晶结构,用红外光谱、荧光和热重等进行了表征。2个配合物都属于三斜晶系,空间群为P1。晶体结构分析表明2个配合物都具有畸变的四面体结构[AgN₃O]。配合物1是一个双核银（Ⅰ）配合物,NO₃^-参与配位;而配合物2是一个配位聚合物,水分子参与配位。     

异构多羧酸配体的两种Zn（Ⅱ）配位聚合物的水热合成和表征

利用异构的半刚性多羧酸配体3,5-二（3-羧基苯氧基）苯甲酸（3-H₃BCP）,3,5-二（4-羧基苯氧基）苯甲酸（4-H₃BCP）和刚性双三唑配体4-（4-（4H-1,2,4-三唑-4-基）苯基）-4H-1,2,4-三唑（L）在相似的水热条件下与金属Zn（Ⅱ）离子反应,制得混合配体的配位聚合物{[Zn（3-HBCP）（L）]·0.5H₂O}_n（1）和[Zn（4-HBCP）（L）_0.5]_n（2）。配合物1为含有双核簇的（4,4）连接的二维网络结构,而配合物2为三重互穿的2D+2D→2D平行网络结构。通过X射线单晶衍射、元素分析、红外光谱、紫外光谱以及荧光光谱其进行了表征。     

异构多羧酸配体的两种Zn(II)配位聚合物的水热合成和表征

利用异构的半刚性多羧酸配体3,5-二（3-羧基苯氧基）苯甲酸（3-H₃BCP）,3,5-二（4-羧基苯氧基）苯甲酸（4-H₃BCP）和刚性双三唑配体4-（4-（4H-1,2,4-三唑-4-基）苯基）-4H-1,2,4-三唑（L）在相似的水热条件下与金属Zn（Ⅱ）离子反应,制得混合配体的配位聚合物{[Zn（3-HBCP）（L）]·0.5H₂O}_n（1）和[Zn（4-HBCP）（L）_0.5]_n（2）。配合物1为含有双核簇的（4,4）连接的二维网络结构,而配合物2为三重互穿的2D+2D→2D平行网络结构。通过X射线单晶衍射、元素分析、红外光谱、紫外光谱以及荧光光谱其进行了表征。     

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).     

Carbonyl complexes of 1,2,4-triazoles : II. The crystal structure of pentacarbonyl-4-methyl-1,2,4-triazolechromium(0), Cr(CO)5(C3H3H5). Chromium-to-triazole π-bonding

The crystal structure of pentacarbonyl-4-methyl-1,2,4-triazolechromium [Cr(CO)₅(C₃N₃H₅)] has been determined by single-crystal X-ray techniques. The compound crystallizes in the space group Pbca with a 10.899(2), b 17.572(2), c 11.877(2) Å and Z = 8. The compound consists of monomeric units in which the chromium atom is coordinated octahedrally to five CO groups and one monodentate coordinating 4-methyl-1,2,4-triazole ligand (CrN 2.111(2) Å). Full matrix least-squares refinement resulted in a final R = 0.025 (R_w = 0.0324). There appears to be no or little π-interaction between the triazole ligand and the chromium atom.     

3-巯基-5-芳香基-4-芳基亚甲胺基-4H-1,2,4-三唑的合成及波谱研究

5-取代-4-氨基-3-巯基-1,2,4-三唑与芳香醛在弱酸性乙醇溶液中反应, 合成了一系列3-巯基-5-芳香基-4-芳基亚甲胺基-4H-1,2,4-三唑(3a～3d)及水溶性的3-巯基-5-(D-葡萄糖-1-基)-4-(4-氯代苯基)亚甲胺基-4H-1,2,4-三唑(3e)新化合物. 以元素分析, IR, NMR, MS实验技术对其结构进行了表征, 并研究其NMR波谱特征.     

Synthesis of group 6 metal carbonyl complexes containing oxygen- and sulfur-functionalized 1,2,4-triazoles

Reaction of RCOCH₂Tz and PhCOCH(CH₂SPh)Tz with M(CO)₆ or M(CO)₅THF results in RCOCH₂TzM(CO)₅ and PhCOCH(CH₂SPh)TzM(CO)₅ (R = phenyl or ferrocenyl, Tz = 1,2,4-triazol-1-yl and M = Mo or W). X-ray crystal structure analyses show that the triazolyl group acts as a monodentate ligand through the exodentate nitrogen atom in these complexes. The electrochemical behavior of these complexes has been investigated by cyclic voltammetry.     

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.     

The chain lengthening of aliphatic aldehydes with the aid of “nucleophilic carbene”

The addition of “nucleophilic carbene” on 1,2,4-triazole bases ($\text{2}$) and aldehydes is decisively influenced by the anion present. 5-(α-Hydroxyalkyl)-1,2,4-triazolium chlorides, formed in the addition reaction of 3-methylthio-1,4-diphenyl-1,2,4-triazolium chloride ($\text{1c}$) with aldehydes, can be easily reduced to 5-alkyl-1,2,4-triazolium iodides ($\text{5}$). Reduction of these with NaBH₄ affords aldehydes by acidic hydrolysis or carboxylic acids by alkaline hydrolysis, the carbon chain of which has been lengthened by one CH₂ group, as compared to the starting aldehyde.     

Structure of zinc complexes with 3-(pyridin-2-yl)-5-(arylideneiminophenyl)-1H-1,2,4-triazoles in different tautomeric forms: DFT and QTAIM study

On the basis of X-ray crystallographic data on molecular crystals of zinc complexes with 3-(pyridin-2-yl)-5-(arylideneiminophenyl)-1H-1,2,4-triazoles, quantum-chemical analysis of the electron density distribution function for these complexes has been performed by Bader’s atoms in molecules method. Topological parameters of electron density at the critical points of coordination and noncovalent bonds have been interpreted, and the bond energies have been estimated using the Espinosa equation. For the solvated complex Zn[(L3)(OAc)₂] · i-PrOH (L3 = 3-(pyridin-2-yl)-5-(benzylideneiminophenyl)-1H-1,2,4-triazole), a variable coordination number of the Zn²⁺ ion has been predicted as a result of dynamic dissociation/formation of an unstable Zn-O coordination bond. For the binuclear [Zn₂(L2)₂] complex (L2 = 3-(pyridin-2-yl)-5-(salicylideneiminophenyl)-1H-1,2,4-triazole), an orbital interpretation of the decrease in the fluorescence quantum yield in tetrahydrofuran and dimethyl sulfoxide as compared with free L2 ligand is presented.     

3－苄基－6－（1－氨基烃基）－1，2，4－三唑并[3,4-b]-1,3,4-噻二唑的合成与波谱表征

3－苄基－4－氨基－5－巯基－1，2，4－三唑与氨基酸在三氯氧磷存在下反应 ，合成3－苄基－6－（1－氨基烃基）－1，2，4－三唑并[3,4-b]－1，3，4－噻二 唑，其结构经元素分析、红外光谱、核磁共振氢谱、碳谱、质谱等确证。这是稠杂 环接氨基酸残基的首次报道。     

Alkylation of 1,2,4-triazole-3-thiols with haloalkanoic acid esters

Alkylation of 4,5-disubstituted 4H-1,2,4-triazole-3-thiols with methyl chloroformate and ethyl chloroacetate chemoselectively afforded the corresponding S-alkyl derivatives, whereas the alkylation of 5-benzyl-4-phenyl-4H-1,2,4-triazole-3-thiol with methyl 3-bromopropanoate gave an inseparable mixture of S- and N-alkylation products. Hydrazinolysis of S-(5-benzyl-4-phenyl-4H-1,2,4-triazol-3-yl) methyl carbonothioate involved anomalous cleavage with formation of the initial 4,5-disubstituted 1,2,4-triazole and methyl hydrazinecarboxylate.