Iminophosphanes and Diphosphenes - Recent Developments

Abstract

Novel iminophosphane derivatives are synthesized by nucleophilic displacement from Cl-P=NMes*. Structures, spectroscopic data, and novel chemical reactions of these compounds are discussed. Furthermore, synthesis of stable cis- and trans isomers of a diphos phene, as well as their mutual interconversion, is reported.     

Synthesis and Reactions of New Fused Heterocycles Derived from 5-Substituted-4-Amino-3-Mercapto-(4H)-1,2,4-Triazole with Biological Interest

The reaction of thiocarbohydrazide with carboxylic acids at the melting temperature allows an improved preparation of 5-substituted-4-amino-3-mercapto 1,2,4-triazoles 1 _{a ? g} . Compound 1 _a reacted with 2-bromopropionic acid to give acid derivative 2 . The latter was reacted with a mixture of acetic anhydride and triethylamine to afford the mesoionic compound 3 . Heating of compound 3 in ethanol gave the ester derivative 4 , which on alkaline hydrolysis in methanol gave ketone derivative 5 . Substituted 1,2,4-triazolo [3,4-b]-6H-1,3,4-thiadiazine 6 _h,i and 7 were synthesized by reaction of 1 _a with acetylacetone, ethyl acetoacetate and chloroacetamide. Heterocyclic systems 8 and 9 were prepared through the reaction of 1 _a with 2,3-dichloro-1,4-naphthoquinone and 2,3-dichloroquinoxaline. In addition, thenoyl isothiocyanate, thenoyl chloride, 2-thiophenecarbaldehyde, and p-chlorophenyl isocyanate reacted with compound 1 _a to afford 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole ring system 10 , 11 , and urea derivative 12 . 1,2,4-Triazolo[3,4-b]-5H-pyrazole derivatives 14 _j,k were prepared through the reaction of compound 1 _a with 3-chloro-2,4-pentandione and ethyl-2-chloroacetoacetate. Compound 14 _j was treated with hydrazine to afford products 15 , 16 , and 17 depending on the type of hydrazine derivative and reaction conditions. Compound 19 was synthesized by refluxing of compound 14 _j with hydroxylamine hydrochloride to afford the corresponding oxime derivative 18 followed by treatment with thenoyl chloride.     

A linear trinuclear cobalt(II) complex with 4-(2-pyridine)-1,2,4-triazole: synthesis,structure and characterization

The linear trinuclear cobalt(II) complex [Co₃(pytrz)₆(H₂O)₆](NO₃)₆ (1) with pytrz = 4-(2-pyridine)-1,2,4-triazole has been prepared and characterized. It crystallizes in the rhombohedral R-3 space group with Z = 3, a = 13.955(2), b = 13.955(2), c = 28.942(9) Å, γ = 120°, V = 4881.2(18) ų. The structure of 1 comprises the cation [Co₃(pytrz)₆(H₂O)₆]⁶⁺, in which linear trinuclear Co(II) units are bridged by six L ligands and have six aqua molecules as terminal ligands. The six free nitrates link the terminal aqua ligands through N–H ··· O hydrogen bonds with C₃ symmetry. 1 was characterized by FT-IR, electronic spectra and magnetic measurements. The variable-temperature magnetic measurements reveal weak anti-ferromagnetic interactions in 1.     

Uranyl-containing heterometallic coordination polymers based on 4-(4’-carboxyphenyl)-1,2,4-triazole ligand: structure regulation through subtle changes of the secondary metal centers

Abstract

Three uranyl-containing coordination polymers, Cd(UO₂)₂(cpt)₄(bdc)(H₂O)₂ (1), Zn(UO₂)₂(cpt)₄(bdc)(H₂O)₂ (2) and UO₂(OH)(cpt) (3) (Hcpt =4-(4’-carboxyphenyl)-1,2,4triazole, H₂bdc =1,4-benzenedicarboxylic acid), have been synthesized under hydrothermal conditions by employing a bifunctional ligand (Hcpt) with both O-donors and N-donors. Compound 1 represents a 3-D framework with the point symbol of (6²·8⁴)(6²·8)₂ by the intersection of two sets of 1-D [Cd₂(UO₂)₂(cpt)₄(bdc)]_n loop chains extended along different directions. Compound 2 exhibits a 2-nodal (3,4)-connected 2-D network with the point symbol (4·6²)₂(4²·6²·8²). Compound 3 shows a 2-D network by the assembly of uranyl dimers and the cpt^- anions. Although 1 and 2 have similar chemical formulas and the same coordination modes of ligands and metal centers, they possess totally different molecular frameworks, derived from the different radii of the secondary metal centers, Cd(II) and Zn(II). In addition, the optimal synthesis condition, thermal stability, luminescent properties, and IR spectra of 1 and 2 were also investigated.     

Synthesis and crystal structures of three new complexes derived from 3-(pyridin-3′-yl)-5-(pyridin-2′′-yl)-1,2,4-triazole

Three new coordination complexes, [Cd₂(ppt)₂(cpba)]?·?(H₂O)₂ (1), [Zn(ppt)₂]?·?(H₂O) (2), and [Zn(MoO₄)(Hppt)] (3) (H₂cpba: 3-(2′-carboxy-phenoxy)-benzoic acid; Hppt: 3-(pyridin-3′-yl)-5-(pyridin-2′′-yl)-1,2,4-triazole), were synthesized under hydrothermal conditions. Their structures have been determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. X-ray diffraction analyses revealed that Cd(II) ions are linked by ppt^? to form a ladder-shaped structure along the a-axis and further displays a 2-D supramolecular architecture with cpba^2? along the c-axis. In 2, each Zn(ppt)₂ fragment is linked by the nitrogen of pyridin-3′-yl from the neighboring Zn(ppt)₂ forming a V-shaped chain. Compound 3 consists of a ladder structure, in which each {MoO₄} unit is a bridge linking three Zn(Hppt)²⁺ fragments.     

Copper(II) coordination polymers constructed from aromatic polycarboxylate and flexible triazole ligands with different spacer lengths: syntheses,structures, and properties

{[Cu₂(btm)₂(Hbtc)(H₂btc)₂(H₂O)]·9.5H₂O}_n (1), [Cu(bte)(H₂btc)₂]_n (2) {[Cu(btp)(H₂btc)₂]·0.25H₂O}_n (3) (btm?=?bis(1,2,4-triazol-1-yl)methane, bte?=?bis(1,2,4-triazol-1-yl)ethane, btp?=?bis(1,2,4-triazol-1-yl)propane, H₃btc?=?benzene-1, 3, 5-tricarboxylic acid) have been synthesized and structurally characterized. 1 features a 1-D double chain, which is interconnected by classical hydrogen-bonding (O–H?O) and π–π interactions to lead to a 3-D supramolecular architecture. 2 and 3 are both 1-D single chains, which are interconnected by π–π interactions to 2-D layer architectures. Elemental analysis, XRD, IR, TG and EPR spectra have been carried out and discussed.     

Synthesis,structural, and spectral studies of diorganotin(IV) complexes with 2–hydroxy-5-methylbenzaldehyde-N(4)-cyclohexylthiosemicarbazone

Three new diorganotin(IV) complexes, [Me₂Sn(L)] (2), [Bu₂Sn(L)] (3), and [Ph₂Sn(L)] (4) [where H₂L (1) = 2-hydroxy-5-methylbenzaldehyde-N(4)-cyclohexylthiosemicarbazone] have been synthesized by reacting the corresponding diorganotin(IV) dichloride with H₂L (1) in absolute methanol in the presence of potassium hydroxide. All the compounds have been characterized by CHN analyses, UV–vis, FT-IR, ¹H, ¹³C, and ¹¹⁹Sn NMR spectroscopy. The molecular structures of H₂L (1) and 2 have been confirmed by single crystal X-ray diffraction analysis. H₂L (1) is found to be in the thiol tautomeric form. The X-ray structure of 2 showed that H₂L is a tridentate ligand and binds to the tin(IV) atom via the phenolic oxygen, azomethine nitrogen, and thiolate sulfur. Complex 2 has a triclinic structure and the coordination geometry of tin(IV) is distorted trigonal bipyramidal. The sulfur and oxygen are in axial positions while the azomethine nitrogen of 1 and two methyl groups occupy the equatorial positions. The C-Sn-C angles determined from ¹J(¹¹⁹Sn, ¹³C) for 2, 3, and 4 are 124.35°, 123.11°, and 123.82°, respectively. The values of δ(¹¹⁹Sn) for 2, 3, and 4 are ?153.4, ?180.59, and ?158.3 ppm, respectively, indicating five-coordinate tin(IV). From NMR data a distorted trigonal-bipyramidal configuration at each tin is proposed.     

Synthesis and study of the structure of new 3d-metal coordination compounds with substituted 2-amino-4(5H)-ketothiophens

A series of new 3d-metal complexes based on 2-amino-3-(1-methylbenzimidazol-2-yl)-4(5H)-ketothiophen (HL¹) and 2-amino-3-(2-benzothiazolyl)-4(5H)-ketothiophen (HL²) were synthesized. Compounds of the general formulas [ML₂] and [M(HL¹)₂Cl₂] (where M = Co²⁺, Ni²⁺, Zn²⁺, Cu²⁺) were prepared by the reaction of the above mentioned ligands with the corresponding acetate (for [ML₂]) or chloride (for [M(HL¹)₂Cl₂]) salts in a methanol or a methanol–chloroform medium. The choice of the anion in the initial metal salt, as well as the selection of the ligand, is crucial for obtaining coordination compounds with a neutral or deprotonated form of the 2-amino-4(5H)-ketothiophens. Thus, in contrast to HL¹, complexes with the neutral form of HL² cannot be obtained under the same conditions. All the complexes were studied by spectroscopic methods and X-ray crystallography (for [CuL¹₂] · H₂O). The coordination polyhedron of the copper atom is formed by four nitrogen atoms from two ligand anions and the geometry of the coordination sphere is intermediate between tetrahedral and square-planar.     

基于一种柔性和角型有机芳香多酸配体的两种3D配位聚合物的合成、结构和荧光性

通过水热合成的方法制得具有三维超分子结构的2种配位聚合物{[Zn（L）（bpa）_0.5（H₂O）₂]·2.25H₂O}_n（1）和{[Cd（L）（H₂O）]·2H₂O}_n（2）,其中,H₃LCl为氯化5-（4-羟基吡啶基甲基）间苯二甲酸,bpa为1,2-二（4-吡啶基）乙烷。这2种化合物的结构通过单晶X射线衍射、红外光谱（IR）、元素分析、热重分析（TG）等方法进行了表征。结构解析表明：化合物1是一种梯型链式结构,并通过链间氢键作用延伸成了3D超分子网络;化合物2为含有大量一维隧道空腔的2D配位网络。此外,研究了这2种化合物的荧光性质。     

基于一种柔性和角型有机芳香多酸配体的两种3D配位聚合物的合成、结构和荧光性

通过水热合成的方法制得具有三维超分子结构的2种配位聚合物{[Zn（L）（bpa）_0.5（H₂O）₂]·2.25H₂O}_n （1）和{[Cd（L）（H₂O）]·2H₂O}_n （2）,其中,H₃LCl为氯化5-（4-羟基吡啶基甲基）间苯二甲酸,bpa为1,2-二（4-吡啶基）乙烷。这2种化合物的结构通过单晶X射线衍射、红外光谱（IR）、元素分析、热重分析（TG）等方法进行了表征。结构解析表明：化合物1是一种梯型链式结构,并通过链间氢键作用延伸成了3D超分子网络;化合物2为含有大量一维隧道空腔的2D配位网络。此外,研究了这2种化合物的荧光性质。     

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).     

Four 1,3-bis(1,2,4-triazol-1-yl)propane-based metal complexes tuned by competitive coordination of mixed ligands: synthesis,solid structure,and fluorescence

Four 1,3-bis(1,2,4-triazol-1-yl)propane (btp)-based transition metal complexes, {[Zn(btp)₃] ?(ClO₄)₂} _n (1), [Zn(btp)₂(dca)₂] _n (2), [Zn(btp)(NCS)₂] (3), and [Mn(btp)₂(NCS)₂] _n (4), have been obtained by introducing small anionic coligands and structurally characterized by single crystal X-ray diffraction, elemental analysis, IR spectra, thermogravimetric curves, and solid luminescence spectra. Structural determinations reveal that the polymeric triple-stranded chain for 1 without coligand is changed into 1-D double-stranded chains for 2 and 4, and discrete binuclear structure for 3. Compared with 1, the mixed-ligand complexes are moderately destabilized for 2 and 4, and slightly enhanced for 3. Additionally, the four solid complexes exhibit strong emissions, suggesting their potential applications as luminescent materials.     

3,5-二烷基-1,2,4-三唑衍生物构筑的两个Cu4I4簇配合物的合成、结构和荧光性质

以3,5-二甲（丙）基-4-氨基-1,2,4-三唑为配体,与CuI在H₂O/MeCN混合溶剂热合成了2个构型不同的Cu₄I₄超分子化合物{[Cu₂（aadmtrz）I₂]·CH₃CN}_n （1）和[Cu₂（dptrz）I]_n （2）（aadmtrz=4-（（1-氨乙基）-氨基）-3,5-二甲基-1,2,4-三唑,dptrz=3,5-二丙基-1,2,4-三唑）,并进行了元素分析,红外,X射线粉末衍射及单晶衍射等表征。2个配合物中Cu₄I₄构型不同,配合物1中,Cu₄I₄簇连结成一个8环椅式-椅式结构,通过配体连接成（4,4）二维菱形格子结构;而配合物2中,Cu₄I₄簇呈畸变的立方烷结构,构成了含有19.5%孔隙率三维孔洞聚合物,其结构可简化为（3,4）-连接的拓朴结构。同时,在常温下研究了2个配合物的固体荧光性质。     

Methoden zur Darstellung von 4-Azido-2(1H)-chinolonen

4-Hydroxy-2-quinolones1 are generally found to be converted to the 4-azidocompounds3 via the 4-chloroquinolones2, the 4-tosyloxyquinolones6, or the 4-aminoquinolones4, respectively. Choice of the reaction conditions and yields depend on the substituent in position 3 of the quinoline nucleus. For comparison the O-analogous coumarin derivatives9 have been studied to give the 4-azidoderivatives11 via the 4-chlorocoumarins10.

     

由MOPIP配体构筑的两种金属配合物的合成、表征及晶体结构(英文)

采用水热法由2种不同金属盐和MOPIP(MOPIP=2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)配体合成了2种新型零维配合物[Cd(MOPIP)3(H2O)9]4n(1)和[Mn(MOPIP)3(H2O)6]2n(2),并对其进行了元素分析、红外光谱表征、热失重和X射线单晶衍射测定。结果表明,每个金属中心离子与来自3个不同MOPIP分子上的6个氮原子进行配位,形成畸变的八面体构型。     

Synthesis,characterization, and biological activity of five new mixed-ligand palladium(II) complexes with ethylenediamine and 4-toluenesulfonyl-L-amino acid dianion

Five new palladium(II) complexes with 4-toluenesulfonyl-L-amino acid dianion and en, [Pd(en)(TsserNO)] (1), [Pd(en)(TsglyNO)] (2), [Pd(en)(TsalaNO)]?·?1.5H₂O (3), [Pd(en)(TsleuNO)]?·?H₂O (4), and [Pd(en)(TspheNO)]?·?2H₂O (5), have been synthesized and characterized by elemental analysis, IR, UV, ¹H NMR, and mass spectrometry. Crystal structure of 1 has been determined by X-ray diffraction analysis. The cytotoxicity was tested by MTT and SRB assays. The results indicate 1–5 exert cytotoxic effects against HL-60, Bel-7402, BGC-823, and KB cell lines and 5 displays the best cytotoxicity. The structure–activity relationships suggest that both amino acid and N-containing ligands have important effects on cytotoxicity.     

Construction of four d10 coordination polymers containing binuclear rings as building blocks from 4′-(2H-tetrazol-5-yl)biphenyl-4-carboxylic acid

Four coordination polymers based on 4′-(2H-tetrazol-5-yl)biphenyl-4-carboxylic acid (H₂TBPC), [Zn(μ₃-TBPC)(H₂O)]_n (1), [Zn(μ₃-TBPC)(Me₂NH)]_n (2), [Cd(μ₃-TBPC)(bpy)]_n (bpy = 4,4′-bipyridine, 3), and [Cd(μ₄-TBPC)(H₂O)]_n (4), were constructed under hydrothermal conditions. The compounds are composed of M₂(TBPC)₂ binuclear ring as a building block. In 1–3, the binuclear rings are interconnected to three different 2-D networks with the same (4·8²) topology. In 4, the binuclear rings are arranged into a 3-D framework with PtS-type topology. The results revealed that the structural diversity is mainly attributed to the coordination geometries of metal ion, the coordination modes of TBPC^2?, and the auxiliary ligand. The thermal stabilities and luminescent properties of 1–4 have also been studied.     

Solvo-thermal Preparation and Characterization of Two CdII Coordination Polymers Constructed From 2,6-(1,2,4-Triazole-4-yl)pyridine and 5-R-Isophthalic Acid (R = Nitro,Sulfo)

Under the solvo-thermal conditions, two novel Cd^II mixed-ligand coordination materials with 2,6-(1,2,4-triazole-4-yl)pyridine(L₁) and aromatic poly-carboxylic acid co-ligands such as 5-R-isophthalic acid (R = nitro, sulfo), namely [Cd(L₁)(NO₂-BDC)(H₂O)₂] · 2H₂O ( 1 ) and [Cd(L₁)(HSIP)(H₂O)] · 4H₂O ( 2 ) (NO₂-H₂BDC = 5-nitroisophthalic acid, H₃SIP = 5-sulfobenzene -isophthalic acid) were successfully prepared. These Cd^II mixed-ligand coordination polymers 1 – 2 have been measured by crystal X-ray analysis, FT-IR spectra and powder X-ray diffraction analyses. In 1 , these seven-coordinate Cd^II atoms (Cd1) are inter-linked by didentate 5-nitroisophthalic acid ligands forming 1D chain structures. In 2 , these L₁ and partially de-pronated HSIP^2– are inter-linked by central Cd^II centers and are arranged into the unique 2D micro-porous metal-organic framework of 2 . Side view of 2 , it is noted that numerous oxygen atoms of un-coordinated carboxylate groups and coordinated SO₃ groups protrude out and decorate the 2D framework of 2 . PXRD patterns of 1 and 2 sample is tested, which is consistent with the simulated PXRD diffraction pattern. Photoluminescence studies show that 2 is highly selective and sensitive to trace elements of Eu³⁺ with excellent K_sv value (7.86 × 10⁴ m ^–1) and low detection limit (5.56 × 10^–2 mM), which also provides a convenient method and platform for real-time detection of Eu³⁺.     

Study on chemical constituents of an edible mushroom Volvariella volvacea and their antitumor activity in vitro

Abstract

Phytochemical investigation of the fruiting body of Volvariella volvacea led to the isolation of a new furanone, 2(5H)-furanone-4-propionic acid named volvafuranone A (1), together with twelve known compounds (2–13). Compounds 2–7, 9–11 were isolated from this mushroom for the first time. The isolated compounds were assessed for their cytotoxicity against four human tumour lines (SGC-7901, PC-3M, MCF-7, HepG-2), and the results showed that compound 2, 3, 12, 13 have significant cytotoxicity with IC₅₀ values of 5.90?μM (HepG-2), 20.72?μM (HepG-2), 27.98?μM (PC-3M) and 23.15?μM (PC-3M), respectively.