Pyrrole‐2‐carbaldehyde Thiosemicarbazonates of Nickel(II) and Palladium(II): Synthesis,Structure, and Spectroscopy

Complexes of pyrrole‐2‐carbaldehyde thiosemicarbazones, [(C₄H₄N⁴)(H)C²=N³–N²(H)–C¹(=S)–N¹HR; R = Ph, H₂L¹; Me, H₂L²; H, H₂L³] with nickel(II) and palladium(II) are described. The reaction of nickel(II) acetate with H₂L¹ in methanol in 1:1 molar ratio yielded a complex of composition, [Ni(κ²‐N³,S‐HL¹)₂] ( 1 ). Likewise reaction of NiCl₂ with H₂L² in 1:1 molar ratio in acetonitrile in the presence of triethylamine base followed by the addition of pyridine did not yield the anticipated [Ni(κ³‐N⁴,N³,S‐L²)(py)] complex, moreover a bis‐square‐planar complex, [Ni(κ²‐N³,S‐HL²)₂] ( 2 ) was formed. However, in the presence of bipyridine (bipy), it yielded the addition product, [Ni(κ²‐N³,S‐HL²)₂(κ²‐N, N‐bipy)] ( 3 ). Reaction of PdCl₂(κ²‐P, P–PPh₂–CH₂–PPh₂) with H₂L³ in toluene in the presence of triethylamine has yielded a complex of stoichiometry, [Pd(κ³‐N⁴,N³,S–L³)(κ¹‐P–PPh₂–CH₂–P(O)Ph₂] ( 4 ). The ligands (HL¹)^– and (HL²)^– are chelating to Ni^II metal atom as anions binding through N³,S‐donor atoms with pendant pyrrole groups, and (L³)^2– is chelating to the Pd^II metal atom as dianion through N⁴,N³,S‐donor atoms (pyrrole is N⁴‐bonded). Fourth site in 4 is bonded to one P‐donor atom of PPh₂–CH₂–P(O)Ph₂, whose pendant –PPh₂ group involves auto oxidation to –P(O)PPh₂ during reaction. These complexes were characterized using analytical data, IR, NMR (¹H, ³¹P) spectroscopy and X‐ray crystallography. Complexes 1 , 2 , and 4 have square‐planar arrangement, whereas complex 3 is octahedral.     

Synthesis and Structural Characterization of Bis(tetrahydro­pyran)calcium Bis[bis(trimethylsilyl)amide]

Transmetalation of Sn[N(SiMe₃)₂]₂ with calcium granules in tetrahydropyran (thp) yields colorless [(thp)₂Ca{N(SiMe₃)₂}₂] ( 1 ) which is soluble in common organic solvents. The calcium center is in a distorted tetrahedral environment with Ca–N and Ca–O bond lengths of 231.08(11) and 240.23(9) pm, respectively. The molecular structure is dominated by steric factors leading to a NCaN bond angle of 119.43(6)°.     

Study of the Interaction of Bis(4‐pyridylthio)methane with Copper(II) Chloride and Bromide

The new ligand bis(4‐pyridylthio)methane (4‐bpytm) ( 1 ) and its complexes [CuX₂(4‐bpytm)] and [CuX₂(4‐bpytm)₂] (X = Cl and Br) ( 2 – 5 ) have been prepared and characterized by elemental analysis, IR‐Raman, UV/Vis spectroscopy. The structures of (4‐bpytm) ( 1 ), [CuCl₂(4‐bpytm)₂] ( 3 ) and [CuBr₂(4‐bpytm)₂] ( 4 ) were determined by single‐crystal X‐ray diffraction analysis. X‐ray analysis of the 1:2 derivatives reveals that the copper atom has a distorted (4 + 2) octahedral environment. The copper atom is coordinated by four nitrogen atoms from four bridging 4‐bpytm ligands and two halogen atoms. The axial Cu–N bonds are considerably longer than the equatorial Cu–N bonds owing to JahñTeller distortion. CuX₂ units are linked to each other through bridging 4‐bpytm ligands to form a 2D interpenetrated coordination polymer. The structural parameters of the 4‐bpytm ligand in these complexes were compared with those of the free ligand.     

两个含双(3,5－二甲吡唑基)甲烷配体的铅(II)配合物的合成与结构表征

Reactions of lead（Ⅱ） nitrate or perchlorate with bis（3,5-dimethylpyrazolyl）methane （dmpzm）, produced two new Pb（Ⅱ） chelated complexes [Pb（dmpzm）2X2] （X=NO3^- 1, ClO4^- 2）. Both compounds were structurally characterized by elemental analysis, IR spectroscopy, thermal analysis, and single crystal X-ray diffraction. Both compounds are mononuclear with a distorted square antiprismatic PbN4O4 coordination geometry incorporating a pair of O,O＇-bidentate anions and N,N＇-bidentate dmpzm ligands. In the crystals of 1 or 2, the methyl or methylene groups of dmpzm ligand interact with the oxygen atoms of nitrates or perchlorates to afford intra- and intermolecular hydrogen bonding, thereby forming a two-dimensional network 1 or a three-dimensional structure 2.     

Efficient Synthesis of Bis(heterocyclyl)methanes

The reaction of pyrrole/furan aldehyde with Grignard reagent and pyrrole/N-methyl pyrrole in sequence allows efficient synthesis of a number of meso-elaborated bis(heterocyclyl)methanes, which are otherwise difficult to obtain through a direct aldehyde condensation route.      

双席夫碱双-(2,4-二羟基苯乙酮)缩肼的合成及其与铜的荧光猝灭反应

报道了一种新的双席夫碱荧光试剂——双—(2，4—二羟基苯乙酮)缩肼的合成；试剂在492.8nm处有一强荧光峰，当有铜离子存在时，可与试剂形成稳定的配合物而使试剂的荧光猝灭；利用此反应建立了一个荧光测定痕量铜的新方法，测定铜的线性范围为0．0～180．0μg／L，检出限0．02μg／L，方法可应用于矿泉水和水中痕量铜的测定。     

Synthesis, structure and characterization of M---Sn (M=Mo, W) bonded heterobimetallic complexes containing bis(pyrazol-1-yl)methane ligands

The reaction of bis(pyrazol-1-yl)methane tetracarbonylmolybdenum(0) or tungsten(0) complexes with RSnCl₃ (R=Ph, Cl) at room temperature yielded heterobimetallic complexes CH₂(Pz)₂M(CO)₃(Cl)(SnCl₂R) (Pz represents substituted pyrazole; M=Mo or W; R=Ph or Cl) in good yields, which have been characterized by elemental analysis, ¹H NMR and IR spectroscopy. The reaction of bis(3,5-dimethyl-4-halopyrazol-1-yl)methane tetracarbonyl tungsten with PhSnCl₃ did not take place even in refluxing CH₂Cl₂. The electronic and steric characteristics of substituents on the pyrazole ring remarkably influence the structures of the products. The structures of CH₂(3,5-Me₂-4-BrPz)₂W(CO)₃(Cl)(SnCl₃) (8) and CH₂(4-BrPz)₂Mo(CO)₃(μ-Cl)(SnCl₂Ph) (17) (Pz: pyrazole) determined by X-ray crystallography show that no chlorine-bridged W---Sn bond is observed in complex 8, while one chlorine-bridged Mo---Sn bond exists in complex 17. The Sn---M bond length is 2.7438(5) Å in complex 8 (W---Sn) and 2.7559(4) Å in complex 17 (Mo---Sn).     

Synthesis, crystal structures and spectroscopic characterization of two neutral heterobimetallic clusters MS4Cu4(pz)6X2 (where M = Mo (1) or W (2), X = Cl (1) or disordered Cl/Br (2), and pz = 3,5-dimethylpyrazole)

The title complexes were synthesized in acetone by the reaction of [n-Bu₄N]₂[MoS₄Cu₄Cl₄] and pz^Me2 for compound 1, and n-Bu₄NBr, [NH₄]₂[WS₄], CuCl and pz^Me2 for compound 2. X-ray diffraction studies of 1 and 2 demonstrate that four of the six edges of the tetrahedral [MS₄]²⁻ core are bridged by four copper atoms, giving a pentanuclear structure MS₄Cu₄(pz^Me2)₆X₂ (M = Mo, W) with the five metal atoms essentially coplanar. The four Cu atoms exhibit two different coordination modes. Each of one pair of mutually trans Cu atoms is coordinated by two (μ₃-S) atoms and two nitrogen atoms of pz^Me2 rings, giving a distorted tetrahedral CuS₂N₂ arrangement. The other two mutually trans Cu atoms are coordinated by two (μ₃-S) atoms, one nitrogen atom of pz^Me2 and one terminal Cl or Br ligand, giving a distorted tetrahedral CuS₂NX unit. In addition to being structurally studied by X-ray diffraction, the title compounds have been characterized by IR, UV–Vis and ¹H NMR spectroscopy. The IR results, which include low-frequency M–S_b stretching bands, are consistent with the X-ray structural analysis and confirm that the [MS₄]²⁻ cores are coordinated through all four sulfur atoms in the complexes 1 and 2.     

3D Luminescent Copper(I) Iodide Coordination Polymer Based on Cu4I4 Clusters and an Ethyl‐bridging Bis(triazole) Ligand

The copper‐iodine based coordination polymer [Cu₄I₂(bmte)]_n ( 1 ) [H₂bmte = 1,2‐bis(5‐methyl‐1H‐1,2,4‐triazol‐3‐yl)ethane] was synthesized using cuprous iodide and a flexible 3‐substituted, ethyl‐bridging bis(triazole) ligand under solvothermal conditions. X‐ray diffraction analysis reveals that compound 1 shows a 3D framework containing Cu₄I₄ clusters and alternating left‐ and right‐handed [Cu(triazole)] helices, which result in a (4,8)‐connected fluorite (flu) topological network. Moreover, compound 1 exhibits orange phosphorescence with the emission maxima at 590 nm in the solid state at room temperature.     

Synthesis and electrochemistry of Group 6 tetracarbonyl (N,N′-bis(ferrocenylmethylene)ethylenediamine)metal(0) complexes

Thermal substitution reaction of Cr(CO)₄(η^2:2-1,5-cyclooctadiene), Mo(CO)₄(η^2:2-norbornadiene), and W(CO)₅(η²-bis(trimethylsilyl)ethyne) with N,N′-bis(ferrocenylmethylene)ethylenediamine (bfeda) yields M(CO)₄(bfeda) complexes which could be isolated from the reaction solution and characterized by elemental analysis, MS, IR, and NMR spectroscopy. In the case of tungsten, W(CO)₅(bfeda) is formed as intermediate and then undergoes the ring closure reaction yielding the ultimate product W(CO)₄(bfeda). The electrochemical behavior of the M(CO)₄(bfeda) complexes was studied by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in dichloromethane with tetrabutylammonium tetrafluoroborate as electrolyte. Constant potential electrolysis of the complexes was performed successively at their peak potentials at 0 °C in their CH₂Cl₂ solution and the electrolysis was followed by in situ recording the electronic absorption spectra in every 5 mC. In the electrolysis of Cr(CO)₄(bfeda), the central Cr(0) is oxidized first and electrolysis continues with oxidations of two ferrocenyl groups until the end of totally three moles of electron passage per mole of complex. In the electrolysis of Mo(CO)₄(bfeda) and W(CO)₄(bfeda) the first oxidation occurs on the central atom forming a short-lived species which undergoes an intramolecular one-electron transfer and is reduced back to M(0) while one of the ferrocene units is oxidized to the ferrocenium cation at the same time. This indicates that the electron is transferred from iron to the central metal atom.     

吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、 表征及催化合成液体聚丁二烯

合成了一系列吡啶双亚胺酰氯三齿Ni(Ⅱ) 配合物(1a~1c, 2a~2c), 通过傅里叶变换红外光谱和元素分析对配合物进行表征, 测定了配合物1a~1c的晶体结构. 3个化合物同属于单斜晶系, 且都具有以Ni原子为中心的近似于C_s对称的扭曲三角双锥构型. 该系列配合物通过倍半乙基氯化铝(EASC)活化, 在20 ℃下对丁二烯聚合表现出良好的催化活性, 得到分子量为4700~5200、 cis-1,4含量为74.8%~77.2%(摩尔分数)的液体聚丁二烯. 通过改变配体的结构和聚合条件, 可在一定范围内调控聚丁二烯的结构和分子量.     

The Coordination Chemistry of the Versatile Ligand Bis(2‐pyridylthio)methane

Bis(2‐pyridylthio)methane [bpytm, (pyS)₂CH₂] and complexes of this ligand with Zn^II, Hg^II, Cu^I, and Ag^I have been prepared and characterised by elemental analysis, by IR, Raman and ¹H and ¹³C NMR spectroscopy, and by X‐ray diffractometry. The ligand is N, N′‐didentate in the Zn^II complexes; N‐monodentate in one Hg^II complex and N, N′‐bis(monodentate) in the other; N‐mono‐N′, S‐didentate in the Cu^I complex; and N, S′‐bis(mono)‐N′, S‐didentate in the Ag^I complex. The structural parameters of the ligand in each coordination mode are compared with those of the free ligand and those of the triiodide salt of the protonated ligand.     

Synthesis of Pharmacologically Active Bis(indolyl) and Tris(indolyl) Derivatives Using Chlorotrimethylsilane

Chlorotrimethylsilane is found to be a comparatively fast and efficient catalyst for carrying out electrophilic substitution reactions of indoles with various aldehydes/ketones/triethylorthoformate, yielding excellent amount of bis(indolyl)methanes/tris(indolyl)methanes. The merits of this protocol are avoidance of any external energy source, minimal reaction time, simple and easy procedure and high yield under solvent free room temperature condition. The versatility of this method has been tested with various aldehydes/ketones and received satisfactory results.     

Syntheses,Spectroscopic, Structural,Fluorescent and Thermal Properties of Bis(saccharinato)copper(II) Complexes with two Bis(pyridylamine) Ligands

Two new copper(II) complexes of saccharinate (sac) with bis(2‐pyridylmethyl)amine (bpma) and N,N′‐bis[1‐(pyridin‐2‐yl)ethylidene]ethane‐1,2‐diamine (bapen), [Cu(bpma)(sac)₂] · H₂O ( 1 ) and [Cu(bapen)(sac)₂] ( 2 ), were synthesized and characterized by elemental analysis, TG‐DTA, X‐ray diffraction, and UV/Vis and IR spectroscopy, respectively. In 1 , the copper(II) ion is coordinated by two N‐bonded sac ligands, and three nitrogen atoms of bpma, in a distorted square‐pyramidal coordination arrangement, whereas the arrangement around the copper ion in 2 is a distorted octahedron with two N‐coordinated sac ligands and a tetradentate bapen ligand. In addition to hydrogen bonding involving the water molecule in 1 , the mononuclear species of 1 and 2 are further connected by weak intermolecular C–H ··· π and C–H ··· O interactions to form a three‐dimensional network. Both complexes are luminescent at room temperature and their emissions seem to be due to ligand‐based π–π* transitions.     

Structural analysis of several W(VI) and Mo(VI) complex perovskites prepared by the polymeric precursors method

We describe in this work the synthesis by the Pechini method of five Mo(VI)- and W(VI)-containing complex perovskites and their structural characterisation by HREM and XRD. The compounds studied, Ba(B_2/3′B_1/3″)O₃ (B′=In and Y; B″=W and Mo) and Sr(In_2/3W_1/3)O₃, were obtained after firing the precursor powders for 8 h at 1200°C. Thermal analysis showed that the formation mechanism of the five perovskites is similar and implies the formation of barium carbonate and barium tungstates or molybdates of different stoichiometries as intermediate phases. Interesting enough, these similar mechanisms yield to materials of a quite different structure. Indeed, Ba(In_2/3Mo_1/3)O₃ and Sr(In_2/3W_1/3)O₃ were found to be disordered perovskites (unit cells: a_p×a_p×a_p and , respectively); on the other hand, two phases coexist in the sample Ba(In_2/3W_1/3)O₃ at the synthesis conditions: an ordered predominant phase (unit cell: 2a_p×2a_p×2a_p) and, as a minor phase, a disordered perovskite (unit cell: a_p×a_p×a_p). Finally, the two yttrium-containing compounds were found to be ordered perovskites (2a_p×2a_p×2a_p).     

Synthesis and Characterization of Bis(Isopropenylphenoxy)Alkanes and Bis(Vinylphenoxy)Alkanes: Two Classes of Highly Reactive,Photopolymerizable Monomers

Abstract

A novel and facile synthesis of difunctional, aromatic vinyl ether analogs is reported. These materials, which are conveniently prepared by the condensation of 4-acetoxystyrene or 4-isopropenylphenyl acetate with α, ω-dihaloalkanes in the presence of base, can be cationically polymerized using diaryliodonium or triarylsulfonium salts as photoinitiators to produce crosslinked polymers. Relative reactivities of the monomers toward cationic polymerization were studied using differential scanning photocalorimetry. The thermal stabilities of the polymers resulting from the photopolymerization of the difunctional, aromatic vinyl ether analogs were studied using thermogravimetric analysis.     

界面缩聚法合成双(烯基环戊二烯基)钛(锆)聚醚的研究

本文通过界面缩聚法利用双(烯基环戊二烯基)钛(锆)二氯化物与二酚反应,制成了16个新的高分子化合物,对它们进行了IR、TGA和分子量的测定。文中还对反应条件与分子量的关系进行了讨论。     

Reactions of Bis(Trifluoromethyl)Phosphine and Tetrakis(Trifluoromethyl)Phosphine with Ruthenium Carbonyl Clusters

Abstract

The reaction of (CF₃)₂P-P(CF₃)₂ with [Ru₃(CO)₁₂] yielded compounds : [Ru₁₄(CO)₁₃{μ-P(CF₃)₂)₂] (1), [Ru₄(CO)₁₄{μ-P(CF₃)₂}₂] (2), and [Ru₄(CO)₁₁{μ-P(CF₃)₂}₄] (3); reaction with [μ-H)₄Ru₄(CO)₁₂] yielded (1) and [(μ-H)₃Ru₄(CO)₁₂{μ-P(CF₃)₂}] (4). The reaction of (CF₃)₂PH with [Ru₃(CO)₁₂] yielded compounds (1) and (4) and compounds (1) and (2) using cluster : ligand ratios of 1:1 and 1:2 respectively. All the compounds have been characterised by X-ray crystallography; a schematic diagram of their structures is shown in Figure 1. The fluxional behaviour of the hydrides in (4) was studied using variable temperature ¹H NMR spectroscopy (see Figure 2). The result of this study was used in the assignment of hydride positions of (4) in the solid state.     

Synthesis and Characterization of Bis(undeca-tungstoferrate) Lanthanates of Potassium

A series of novel rare earth complexes with 11-tungstoferrate as ligand, K15Ln(FeW11 O39)2 .xH2O(Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er or Yb) were prepared and characterized by elemental analyses, IR, UV-vis, polarograms, magnetic susceptibility and thermal measurement.Keywords Heteropoly complex, Rare earth complex, Synthesis, Bis(undecatungstoferrate) lanthanates of potassium