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1.
Preparations are described of several monometallic complexes (bipym)PtR2 [bipym = 2,2′-bipyrimidyl; R = Me, CF3, Ph, 1-adamantylmethyl (adme); R2 = (CH2)4] and bimetallic analogues R2Pt(μ-bipym)PtR′2 [R = R′ = CH3, C6H5, adme; R = CH3, R′ = Ph, adme, CF3]. IR, 1H NMR and UV/visible spectroscopic characteristics of the two modes of bipyrimidyl coordination are discussed.  相似文献   

2.
Manganese(II) and copper(II) complexes of the type M(ligandH)2 with some nitrogenoxygen and nitrogensulphur donor ligands (HL) viz. phenylpyruvic acid semicarbazone (ppysc), 4-methylphenylpyruvic acid semicarbazone (4-mppysc), phenylpyruvic acid thiosemicarbazone (ppytsc) and 4-methylphenyl pyruvic acid thiosemicarbazone (4-ppytsc), have been synthesised. All the complexes have been characterised by magnetic moment measurements, IR electronic and electron spin resonance special studies. All the ligands behave as tridentate.  相似文献   

3.
The new heterobimetallic compounds Cp3U[OCM(CO)2Cp′] containing uranium and group VI transition metals are synthesized from Cp3UCl and Na[M(CO)3Cp′] or from Cp3UCH3 and H[M(CO)3Cp′] (M = Mo, W; Cp = C5H5; Cp′ = C5H5 or C5Me5). In a same manner, the trimetallic Cp2U[OCMo(CO) 2Cp]2 is obtained starting from Cp2U(NEt2)2 and H[Mo(CO)3Cp]. All these complexes exhibit low CO stretching frequencies characteristic of isocarbonyl linkages between uranium and Mo or W atoms.  相似文献   

4.
New Pd(II) and Pt(II) 3,6-bis(2′-pyridyl)pyridazine (dppn) mononuclear complexes of the type M(dppn)Cl2 were prepared and characterized. From M(dppn)Cl2, the bimetallic homonuclear complexes M(dppn)MCl4 were prepared by reaction with Pd(PhCN)2Cl2 or K2PtCl4. Bimetallic heteronuclear species of the type M(dppn)M′Cl4, were prepared reacting the mononuclear complexes with the stoichiometric amount of M′Cl2 (M′ = Cu, Co, Ni). All the described reaction give product in high yield. The isolated compounds, almost completely insoluble in most organic solvents, were characterized by elemental analysis, IR, ESR, reflectance spectra, and magnetic moment measurements. On the basis of these data the geometries around the metals are discussed.  相似文献   

5.
Complexes of uranyl chloride and uranyl nitrate of the type UO2X2·2L and [UO2X22L′], where X = Cl or NO3 and L = N,N′-tetramethylthiourea (TMTU); N,N′-dimethylthiourea (DMTU); monomethylthiourea (MMTU), monoethylthiourea (METU), pyridine-2-thiol (PYT) and L′ = 4,6-dimethylpyrimidine-2-thiol (PYMT), have been prepared. The complexes were characterised on the basis of IR spectroscopy and by elemental analysis. In some cases Raman spectra are also reported.  相似文献   

6.
Three new palladium(II) complexes of formula [Pd(bipy)(XX)] [where bipy is 2,2′-bipyridine and XX are dianions of catechol (CAT), 4-tert-butylcatechol (BCAT) and 3,4-dimercaptotoluene (DMT)] have been prepared and characterized by physical methods. A ligand-ligand charge-transfer band in each complex was observed between 16–21 kK (εmax = 1500–2200 1 mol?1 cm?1) which is negatively solvochromic. These palladium(II) complexes in dimethylformamide photosensitize the formation of singlet oxygen and their ability to photosensitize triplet oxygen (3O2) to singlet oxygen (1O2) are compared with analogous platinum(II) complexes. In addition, 2,2′-bipyridine-platinum(II) complex of 3,4-dimercaptotoluene also undergoes self-sensitized photooxidation.  相似文献   

7.
Novel neutral biimidazolate or bibenzimidazolate palladium(II) and platinum(II) complexes of the type M(NN)2(dpe) [M = Pd, Pt; (NN)22? = BiIm2?, BiBzIm2?. dpe = 1,2-bis(diphenylphosphino) ethane] have been obtained by reacting MCl2(dpe) with TI2(NN)2. Complexes M(NN)2(dpe) which are Lewis bases react with HClO4 or [M(dpe)(Me2CO)2](ClO4)2 to yield, respectively, mononuclear cationic complexes of general formula [M{H2(NN)2](dpe) (M = Pd, Pt; H2(NN)2 = H2BiIm, H2BiBzIm) and homobinuclear palladium(II) or platinum(II) cationic complexes of the type [M2{μ - (NN)2}(dpe)2](ClO4)2. Reactions of M(BiBzIm)(dpe) with [Rh(COD) (Me2CO)X](ClO4) render similar heterobinuclear palladium(II)-rhodium(I) and platinum(II)-rhodium(I) cationic complexes, of general formula [(dpe)M(μ-BiBzIm)Rh(COD)](ClO4) (M = Pd, Pt; COD = 1,5-cyclooctadiene). Di- and mono-carbonyl derivatives [(dpe)M(μ-BiBzIm)Rh(CO)L](ClO4) (M = Pd, Pt; L = CO, PPh3) have also been prepared. The structures of the resulting complexes have been elucidated by conductance studies and IR spectroscopy.  相似文献   

8.
I. Gosney  D. Lloyd 《Tetrahedron》1973,29(12):1697-1710
Stable crystalline arsonium ylides have been prepared by thermal decomposition of diazo compounds in the presence of triphenylarsine, and by condensation reactions of reactive methylene compounds with triphenylarsine oxide. The spectra of these ylides, and their reactions with benzaldehydes are discussed. Like other stabilised arsonium ylides they give alkenes rather than epoxides in Wittig reactions. They are generally more polar than their phosphonium analogues and also are more reactive in the Wittig reaction. With diphenylcyclopropenone some more reactive arsonium ylides form α-pyrones.  相似文献   

9.
The neutral tris-2,2′-bipyridine(bipy) and 1,10-phenanthroline(phen)compounds Mbipy3 and Mphen3 can be made conveniently in high yield by sodium amalgam reduction of the chlorides of Ti, Zr, Hf, V, Nb, Ta, Cr or better, for Mo, W and Re, the respective adducts MoCl4L, WCl4L and ReCl4(THF) in tetrahydrofuran containing the ligands. The Cr and Mo compounds can also be obtained from the dimeric acetates M2(CO2Me)4. For vanadium, similar compounds have been obtained from 2,2′-dipyridylamine, 2,2′-dipyridyldisulfide and di-t-butyldiimine. Reduction of VCl3 in THF containing one equivalent of 2,2′-bipyridine under CO gives the carbonyl V(CO)4bipy. Interaction of Vbipy3 with NO and CH3I give respectively, V(NO)bipy3 and [V(CH3)I(bipy)].  相似文献   

10.
Equilibria between a series of asymmetric diaminodiamides and Ni(II) in aqueous solution have been studied by potentiometric and spectrophotometric methods. The ligands were S,R,S- and S,S,S-N,N′-dialanylpropylenediamine (DAPN), S,S-N,N′-dialanylethylenediamine (DAEN), R-N,N′-diglycylpropylenediamine (DGPN), and N,N′-diglycylethylenediamine (DGEN). At lower values of pH the complexes NiL2+ and in some cases NiL2+2 were formed. Spectral data indicated that both of these were octahedral. At higher pH the two amide protons were lost and square planar complexes were formed. The diastereomeric DAPN ligands showed stereoselectivity in the equilibrium constants for deprotonation and formation of the square planar complexes. Comparison of optical rotatory dispersion curves and absorption spectra for the various complexes permits partial assignment of structures.  相似文献   

11.
New copper(II) complexes of general formula, Cu(ONS)B (ONS = the di-negatively charged Schiff base, S-benzyl-β-N-(2-hydroxyphenyl) methylendithiocarbazate; B = pyridine, 2,2′-dipyridyl or 1,10-phenanthroline) have been synthesized and characterised by magnetic and spectroscopic measurements. The complex, Cu(ONS)py is four-coordinate and square-planar. Magnetic and spectroscopic data support a five-coordinate, presumably, a trigonal-bipyramidal structure for the [Cu(ONS)dipy] and (Cu(ONS)phen] complexes  相似文献   

12.
The reactions of K2PtCl4 with the aminoacids, S-methyl-L-cysteine, S-ethyl-L-cysteine, S-benzyl-L-cysteine, S-para-nitro-benzyl-L-cysteine, S-diphenyl-methyl-L-cysteine, S-tribenzyl-L-cysteine and S-4′,4′-dimethoxy-diphenylmethyl-L-cysteine were studied in neutral or acidic aqueous solutions. Complexes of the formulae PtLCl2, [PtL2]Cl2 and Pt(L-H+)2, where L = aminoacid, were isolated in the solid state and their structures investigated with elemental analysis, conductivity measurements, IR, 1H NMR and 13CNMR spectra. The results show that the coordination sites of Pt(II) with the amino-acids are the N and S atoms, producing two diastereoisomers around the chiral sulphur atom, which were identified in the 1H NMR and 13CNMR spectra. The complexes PtLCl2 further react with the nucleosides guanosine and inosine. The complexes [PtL(nucl)2]Cl2 were isolated from these reactions and studied with the same methods. They showed a PtN7 bonding with the nucleosides and retained the N, S bondings with the aminoacids. As a result of the higher trans influence of S than N, the nucleoside molecule coordinated to the metal through N7 and trans to S has a weaker bond strength than the other, as it is revealed from the 1H NMR and 13C NMR spectra of these complexes.  相似文献   

13.
Tributylgermanium oximates have been prepared by reactions (a) of tributylgermanium chloride with (i) oximes in the presence of a base, (ii) sodium oximates, and (iii) organotin oximates, as well as (b) of tributylgermanium ethoxide and oxide with oximes.The derivatives have been characterised by elemental analyses, molecular weight measurements and IR spectra. Their reactions have been studied in detail.  相似文献   

14.
Perfluoronorbornadiene reacts with the compounds [M(PPh3)4] (M = Pt, Pd) and [IrCl(CO)(PMePh2)2] to give the adducts [(C7F8)M(PPh3)2] and [(C7F8)IrCl(CO)(PMePh2)2] in which one of the double bonds is coordinated to the metal atom. The platinum complex reacts further with [Pt(PPh3)4] to give [(C7F8){Pt(PPh3)2}2] having both double bonds coordinated to a Pt atom. The carbonylmetal anions [M?] react to form the mono-substitution products [(C7F7)M] (M = Mn(CO)5, Re(CO)5, Ir(CO)2(PPh3)2, Rh(CO)2(PPh3)2), but the use of an excess of [Fe(CO)2(η-C5H6)]? leads to substitution of one fluorine atom on each of the double bonds. The complex having M = Mn(CO)5 reacts with [Pt(PPh3)4] to afford the derivative [(C7F7){Mn(CO)4(PPh3)}{Pt(PPh3)2}], and the compound where M = Ir(CO)2(PPh3)2 undergoes an oxidative addition reaction with acetyl chloride. Oxidative coupling products have been isolated on UV irradiation of a mixture of perfluoronorbornadiene and [Fe(η4-CH2CRCHCH2)(CO)3] (R = H, Me), and under similar conditions the reaction with Fe(CO)5 affords [(C7F8)Fe(CO)4] in very low yield.  相似文献   

15.
Styrene-divinylbenzene copolymer resins containing a series of diethylenetriamine derivatives have been prepared and characterized. The multidentate ligands are covalently bound to the polymer matrix without causing inter- and intrastrand bridging structures. The properties of the present chelating resins have been examined with respect to the uptake of transition metal ions.  相似文献   

16.
Palladium(II) malonato complexes with heterocyclic ligands have been synthesized and characterized by spectroscopic and biological studies. The compoun  相似文献   

17.
Six dimeric copper(II) complexes of the type Na[Cu2(D)(L)], where D = glycylglycinate dianion, and HL = imidazole and 2-methylimidazole; D = glycyl-L-tyrosinate dianion, HL = imidazole and benzimidazole; D = glycyl-L-phenylalaninate dianion, and HL = imidazole; and D = glycyl-L-tryptophenate dianion, and HL = benzimidazole, have been prepared. They were characterized by IR, visible absorption, and EPR spectroscopy. The EPR data indicated their complete dimeric behaviour in basic solution with two Cu(II) ions in close proximity of <7Å with imidazolate, 2-methyl-imidazolate, and benzimidazolate bridges.  相似文献   

18.
3,3′-Dicarbomethoxy-2,2′-bipyridyl(DCMB)reacts with K2MCl4(M = Pd,Pt) to give M(DCMB)Cl2 and with RhCl3 to give the cis-[Rh(DCMB)2Cl2]+ ion. Attempts to prepare the tris (DCMB) complex with Rh(III) and analogous Co(III) complexes were unsuccessful.  相似文献   

19.
Three types of the novel polymer ligands in which 6,8,15,17-tetramethyl-dibenzo-5,9,14,18-tetraaza-cyclotetradecene (L) is present as an integral part of the polymer backbone have been prepared. These polymer ligands are oligomers whose polymerization degree may be about five. Their complexing abilities and extractabilities for copper(II) and nickel(II) have been investigated. Among the polymer ligands, Poly-L3, which contains triethyleneglycol bis(p-phenylene) group as a linkage group, was found to be an excellent extractant for copper(II).  相似文献   

20.
K. J. Ewing  S. I. Shupack 《Polyhedron》1985,4(12):2069-2072
The preparation and characterization of new tetrahalodimolybdenum(II) complexes with alkyl-substituted pyridines is described. IR and visible data are used to infer structural information with respect to previously prepared complexes of this type.  相似文献   

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