BisN(chlorophenyl)dithiocarbamato complexes of cobalt(II), nickel(II), palladium(II) and platinum(II)

Summary Cobalt(II), nickel(II), palladium(II) and platinum(II) complexes witho-(OCD),m-(MCD) andp-chlorophenyldithiocarbamate (PCD) ligands have been synthesised and characterised by chemical analyses, molecular weight determinations, conductance measurements, electronic and i.r. spectral studies. The thermal behaviour of the complexes has been studied by t.g. and d.t.a. techniques in a static air atmosphere and heats of reaction of different decomposition steps have been calculated from the d.t.a. curves. The thermal decomposition products of the complexes were identified by elemental analyses and i.r. spectra.     

Polymethine dyes based on (benzo-15-crown-5) thiazole

Several monomethinecyanine, merocyanine and styryl dyes were synthesized using a 5,6-(1,4,7,10,13-pentaoxacyclotridecane)-benzothiazole derivative as the starging reageni. A study was made of their spectral characteristics and the effect which complexing with alkaline and alkaline-earth metal salts had on their chromaticity.Organic Chemistry Institute, National Academy of Sciences of Ukraine, Kiev. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 992–996. Original article submitted March 12, 1996.     

The Syntheses and crystal structures of trans-dichlorobis (10-thiabenzo-15-crown-5)-palladium(Ⅱ)and trans-dichlorobis-(10-selenabenzo-15-crown-5)palladium(Ⅱ)

The preparation and X-ray crystal structures of the adducts of 10-thiabenzo-15-crown-5 and 10-selenabenzo-15-crown-5 with PdCl2 are reported. [PdCl2(C14H20O4S)2] (1): or-thorhombic, space group Pbca with cell dimensions of a=17.285(5), 6=8.354(3), c=21.689(4) A, K=3131.9 A3, Z=4;R=0.0330 for 2301 reflections with I > 3o(I), [PdCl2(C14H2oO4Se)2] (2): monoclinic, space group P21/n with cell dimensions of a=18.928(4), b=8.912(3), c=9.813(2) A, β=96.90(2)0, V=1643.4 A3, Z=2; R=0.0289 for 2617 reflections with I> 3σ(I), Both complexes are monomeric, square-planar palladiurn(Ⅱ) compounds with the Pd(Ⅱ) ion situating on a crystal-lographic inversion centre, and the crown ligands all adopt the axial coordination with the Pd-S bond of 2.3233(7) A and the Pd-Se bond of 2.4357(3) A. Their complexing characteristics are discussed in brief.     

N-aminorhodamne complexes of palladium(II), palladium(IV) and platinum(II)

Summary TheN-aminorhodanine (L) complexes: PdLX, (X = Br or I), ML_1.5Cl₂ (M = Pd or Pt), PtL₂X₂ (X = Br, I or ClO₄), PdL₃(ClO₄)₂, PdL_1.5Cl₄ and PdL₃(ClO₄)₄ have been prepared and investigated. The ligand is bonded to the metal ion through the aminic nitrogen atom as monodentate or through this atom and the thiocarbonylic sulphur atom when it acts as chelating or bridging ligand. The carbonylic oxygen atom is never coordinated.     

Syntheses, spectroscopic characterization and metal ion binding properties of benzo-15-crown-5 derivatives and their sodium and nickel(II) complexes

New benzo-15-crown-5 derivatives containing nitro, amine and imine groups were prepared. Nitro compound (1) was prepared after the reaction?4′,5′-bis(bromethyl)benzo-15-crown-5 and o-nitrophenol in the presence of NaOH. After reduction process by using hydrazine hydrate and Pd/C amine compound (2) was formed. New crown ether imine compounds (3–5) were synthesized by the condensation of corresponding crown ether diamine (2) with salicylaldehyde derivatives. Sodium complexes of the crown compounds (1a–5a) form crystalline 1:1 (Na⁺: ligand) complexes with sodium perchlorate. Nickel(II) complexes (3b–5b) with 1:1 (Ni²⁺:ligand) stoichiometries were also been synthesized from the Schiff bases (3–5). The results indicated that the Schiff base ligands coordinated through the azomethine nitrogen and phenolic oxygen. The extraction ability of compounds (1, 3, 4 and 5) were also evaluated in chloroform by using several alkali and transition metal picrates such as Li⁺, Na⁺, K⁺, Cr³⁺, Mn²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Pb²⁺.     

The coordination chemistry of simple phospholes: Complexes of nickel(II), palladium(II) and platinum(II)

The reactions between four very simply substituted phospholes and the chlorides of Ni(II), Pd(II) and Pt(II) are described. The phospholes 1-phenylphosphole, 3-methyl-1-phenyl-phosphole and 3,4dimethyl-1-phenylphosphole all readily form bis-complexes of formula L₂MCl₂ [L = phosphole ligand and M = Ni(II), Pd(II) or Pt(II)] or tris-complexes of formula L₃MCI₂. 1-n-Butyl-3,4-dimethylphosphole appears to form stable complexes only with Ni(II). Evidence is put forward which indicates that the L₂MCl₂ complexes exist in a four-coordinate, square-planar monomeric/five coordinate equilibrium while the L₃MCl₂ complexes are primarily the ionic species [L₃MCl]⁺ Cl^? in solution. Comparisons are made with the behaviour of other simple phospholes which do not form Ni(II) complexes and the results are discussed briefly in terms of both aromatic and non-aromatic phosphole models.     

New nickel(II), copper(II), platinum(II) and palladium(II) complexes of a multidentate sulfur–nitrogen chelating agent

A new, potentially polydentate sulfur–nitrogen chelating agent, 2,6–bis(N-methyl-S-methyldithiocarbazato)pyridine (L) has been synthesized and characterized. With nickel(II) salts, the ligand yields complexes of empirical formula NiLX2·nH2O (X=Cl−, NCS− or NO3−; n=0 or 1) in which it behaves as a quadridentate NSSN chelating agent, coordinating to the nickel(II) ion via the two amino nitrogen atoms and the two sulfur atoms. Magnetic and spectral evidence support a distorted octahedral structure for these complexes. The ligand reacts with copper(II), platinum(II) and palladium(II) salts to yield homo-binuclear complexes of general formula [M2LX4]·nSol (M=CuII, PtII or PdII; X=Cl− or Br−; n=0.5, 1 or 2; Sol=H2O, MeOH or MeCOMe), in which each of the metal ions is in a square-planar environment. These complexes have been characterized by a variety of physicochemical techniques. This revised version was published online in June 2006 with corrections to the Cover Date.     

Synthesis and characterization of 1-Methyl-4-mercaptopiperidine complexes of nickel(II), palladium(II) and platinum(II)

Summary Complexes of formulae Ni(HRS)₂X₂ (X=Cl or Br), M(HRS)₂Y₂ (M=Ni or Pd; Y=NO₂ or C1O₄), Pd(HRS)X₂ (X=Cl, Br or I), Pt(HRS)X₂ (X=Cl or Br), Pt(HRS)₂(ClO₄)₂ and M(RS)₂ (M=Pd or Pt) where HRS and RS denote 1-methyl-4-mercaptopiperidine in the zwitterionic or in the thiolato form, respectively, have been prepared and characterized. In all the complexes the ligands are coordinated exclusively through sulphur. Polymeric structures consisting of square-planar geometry with sulphur-bridged metal atoms are proposed in each case.     

苯并-15-冠-5四溴合铟酸钾配合物的晶体结构

苯并-15-冠-5-四溴合铟(III)酸钾,KInBr~4(C~14H~20O~5)~2,晶体属单斜晶系,空间群为C~2h^5-P2~1/n,晶胞参数a=14.402(3),b=15.082(3),c=17.262(5)A,β=93.42(2),Z=4.非氢原子的位置由Patterson函数及Fourier合成法找出,经全矩阵最小二乘法修正R=0.057.结构分析表明K^+和两个苯并-15-冠-5(B-15-C-5)分子直接配位,对阴离子为InBr~4^-,具有四面体构型.InBr~4^-与配阳离子K(B-15-C-5)~2^+依靠静电引力结合为离子对.由此说明,In(III)在过量KBr存在下可以被B-15-C-5定量地萃取至有机相中.     

Dioxygen affinities and catalytic oxidation performance of cobalt（Ⅱ） hydroxamates with benzo-15-crown-5 pendants

The oxygenation constants(Ko_2)of cobalt(Ⅱ)hydroxamates(CoL_2~1-CoL_2~3)with benzo-15-crown-5(B15C5)pendants were measured over the range of-5 to 20℃,and the values of thermodynamic parameters(ΔH~0 andΔS~0)were calculated based on these(No_2)values.Meanwhile,these crowned complexes were employed to the oxidation for p-xylene to p-toluic acid with air at 110Δunder normal atmospheric pressure.The effects of B15C5 pendant and the length of chain bonded to B15C5 in these complexes on the O_2-binding capabilities and oxidation for p-xylene were investigated with the comparison of crown-free analogues CoL_2~4.     

Synthesis, luminescence and ion-binding properties of palladium(II) complexes with 1,2-bis[di(benzo-15-crown-5)phosphino]ethane (dbcpe)

A series of palladium(II) complexes with 1,2-bis[di(benzo-15-crown-5)phosphino]ethane ligand (dbcpe), [Pd(dbcpe)X2] (X = Cl 1, Br 2 and I 3), have been successfully synthesised and characterised. The X-ray crystal structure of dbcpe has also been determined. The cation-binding properties of the complexes have been studied and the stability constants with alkali metal cations determined. The crown-free analogue of dbcpe, 1,2-bis[bis(3,4-dimethoxyphenyl)phosphino]ethane (ddmppe), and the related complexes have also been prepared and comparison studies have been made.     

1,2-polybutadiene complexes with d8 pseudo-square-planar transition-metal salts based on nickel(II), palladium(II), and platinum(II)

The effects of four d⁸ transition-metal complexes from Group 10 on the thermal, mechanical, optical, and spectroscopic properties of atactic 1,2-polybutadiene are compared, in addition to their ability to induce gelation. Olefin coordination and subsequent metal-catalyzed chemical crosslinking occur much more quickly, and to a greater extent, at ambient temperature with PdCl₂(CH₃CN)₂ than with PtCl₂(C₆H₅CN)₂. Alkene side groups in the polymer attack the pseudo-square-planar metal center (i.e., Pd²⁺ or Pt²⁺) from above or below the plane of the coordinatively unsaturated low-molecular-weight organometallic complex and displace neutral acetonitrile or benzonitrile ligands via an associative mechanism. Gelation occurs much more quickly with Pd²⁺ than with Pt²⁺, and the ambient-temperature elastic modulus of solid polybutadiene/palladium complexes increases significantly, without high-temperature annealing, so that a weak rubbery polymer is transformed into a glass via 3 mol % Pd²⁺. Alkene functional groups in the side chain of the polymer do not coordinate to bis(dimethyl)glyoximatonickel(II) at ambient temperature because (1) it is difficult to displace anionic dimethylgloxime ligands that are bidentate; (2) these planar nickel complexes with C_2h symmetry are stacked along the c axis via interlocking methyl groups on adjacent molecules; and (3) there is a lack of π back-bonding between d_xy on Ni(II) and empty π* antibonding orbitals of CC, which typically stabilizes olefin complexes with pseudo-square-planar d⁸ metal centers. Pseudo-octahedral nickel(II) chloride hexahydrate does not form a complex with the polymer, in agreement with some macroscopic properties of these materials. The observed trend in the transition-metal-modified properties of atactic 1,2-polybutadiene in the solid state and in the gel state is Pd(II) > Pt(II) ≫ Ni(II). © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2270–2285, 2004     

苯并-15-冠-5和二苯并-18-冠-6萃取分离铟(III)的研究

本文用斜率法、饱和法以及通过与萃取合物相对应的冠醚配合物晶体的制备及其性质研究, 探讨了In^3^+的萃取机理, 测定并计算了表观萃取平衡常数, 将此萃取体系应用于铟和某些体系应用于铟和某些金属离子的萃取分离, 亦获得较好的结果.     

Radiation-chemical changes of benzo-15-crown-5 in chloroform

NMR, IR and MS were used for identification of major products of radiolysis of benzo-15-crown-5 in chloroform. The crown ether exhibits high affinity towards inorganic products of radiolysis of chloroform resulting in the formation of complexes.     

Complexation of tetrafluoroboric acid with benzo-15-crown-5

Russian Chemical Bulletin - The extraction of tetrafluoroboric acid from aqueous solutions to a solution of benzo-15-crown-5 (B15С5, 1 mol L-1) in chloroform is shown to occur due to...