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1.
Antonio C. Fabretti Giancarlo Franchini Wanda Malavasi Giorgio Peyronel 《Polyhedron》1985,4(6):989-992
Some palladium(II) halide complexes with 2,5-dimethyl- (DTZ), 2-amino- (ATZ), 2-amino-5-methyl- (MATZ), 2-ethylamino- (EATZ) and 2-mercapto-5-methyl-1,3,4-thiadiazole (MTTZ) have been prepared and studied: PdX2 · 2L (L = DTZ, ATZ, MATZ : X = Cl, Br, I; L = EATZ: X = Br, I; L = MTTZ: X = I), PdCl2 · 2.5EATZ, PdCl2 · 3MTTZ, PdBr2 · 1.5MTTZ and PdX2 · L (L = DTZ, ATZ, MATZ, EATZ: X = Cl, Br; L = MTTZ: X = Cl(H2O), Br). In the PdX2 · 2L, PdCl2 · 2.5EATZ and PdCl2 · 3MTTZ complexes the palladium ions are cis-(2X, 2L)-coordinated, the coordination sites being Nring for DTZ, NR2 for ATZ, MATZ, EATZ and C = S for MTTZ. PdBr2 · 1.5MTTZ may be formulated as cis[PdBr2-2L] · [PdBr2 · L]. In the PdX2 · L complexes the ligand very likely acts as bidentate by using a ring-nitrogen atom as the second coordination site. 相似文献
2.
A series of Cu(II) complexes of the thiosemicarbazone, 3-azabicyclo[3.2.2]-nonene-3-thiocarboxylic acid 2-[1-(2-pyridinyl)ethylidene]hydrazide(HL) and the corresponding N-oxide (HLO) have been prepared and characterized. Both ligands undergo deprotonation and appear to coordinate via the thione sulfur, the imine nitrogen and the pyridyl nitrogen (or N-oxide oxygen). A single anionic ligand such as Cl?, Br?, NCS? and N?3 completes the bonding to the Cu(II) center of these 4-coordinate complexes. When the complexes are prepared using Cu(II) perchlorate, the solids isolated contain a neutral thiosemicarbazone ligand as well as the deprotonated ligand. The solids are primarily characterized by IR, electronic and electron spin resonance spectroscopy. In addition, electronic and ESR spectra of their chloroform solutions were recorded. Most of the solids (except the nitrates) were unaltered upon dissolution. Simulation of the solution ESR spectra was used to estimate the coupling constants of the various coordinated nuclei. 相似文献
3.
Passage of CO through solutions of complexes (C6F5)2CoL2 gives carbonyl derivatives (C6F5)2CoL2(CO) (L2 = 2 PEt3, 2 P-n-Bu3, 2 PPh3, Ph2PCH2CH3PPh2). The properties of these compounds are described.The compounds are also produced by treating solutions of (C6F5)2Co-(dioxane)2 with CO, but a simultaneous reduction to (C6F5)Co(CO)4 takes place. Treatment of the latter complex with monodentate ligands gives substitution products (C6F5)Co(CO)3L (L = PEt3, P-n-Bu3, PPh3) all of which are monomeric, whereas the addition of Ph2PCH2CH2PPh2 gives the dimer (C6F5)(CO)2CoLLCo(CO)2(C6F5). The properties of these compounds are discussed. 相似文献
4.
The reaction of nickel(II)chloride with γ-mercapto-propylamine in ethanolic solution gives the complex [Ni3(MPA)4]Cl2(MPA=NH2-(CH2)3-S). The complexes [Ni3(MPA)4]X2(X=Br, I, ClO4) can be synthesized from the chloride complex by addition of the sodium salt in aqueous solution. The crystal structure consists of discrete divalent trinuclear cations and chloride anions. Each sulphur atom of the ligand acts as a bridge between two nickel atoms, and the nitrogen atoms complete the coordination around the terminal nickel atoms. The geometry around the metal atoms is square-planar. The electronic and IR spectra of the complexes [Ni3(MPA)4]X2(X=Br, I, ClO4) indicate that all these compounds are composed of the [Ni3(MPA)4]2+ and X? ions. 相似文献
5.
(1,5-Cyclooctadiene) (4-substituted pyridinium 2-pyridylcarbonylmethylide)- rhodium(I) perchlorates, [Rh(COD)(C5H4NC(O)C?H+C5H4X-4)]ClO4 [COD = 1,5-cyclooctadiene; X = CH3C(O), CH3OC(O), C6H5, CH3, and H], have been prepared. They are shown to have the geometry with coordination by the pyridyl nitrogen and carbonyl oxygen atoms of the ylide ligands and to exhibit intramolecular rearrangement of coordinated COD in chloroform, methanol, and dimethyl sulphoxide based on IR and 1H NMR spectroscopies. Although the ylides have exhibited fluorescence bands due to an intramolecular charge-transfer transition and phosphorescence bands due to a carbonyl 3(n?π*) transition, the complexes have given emission bands due to the metal-to-ylide ligand charge-transfer transition. A.single crystal X-ray crystal structure has been determined for [Rh(COD)(C5H4NC(O)C?H+C5H4CH3-4)]ClO4. The crystals are monoclinic, space group P21/n with cell dimensions a = 14.887(3), b = 20.274(4), c = 6.966(1) Å, β = 96.13(1)°, and Z = 4. The structure has been refined by a block-diagonal least-squares method to final R = 0.060 for 2997 independent reflections with |Fo| > 3σ(F). The ylide carbon-pyridinium nitrogen bond distance is 1.420(10) Å. The bonded distances from rhodium to the midpoints of the double bonds of COD are 1.982(11) and 2.014(12) Å. 相似文献
6.
The basicity constants of N,N′-bis(β-carbamoylethyl)ethylenediamine, N,N′-bis(β-carbamoylethyl)trimethylenediamine, N,N′-bis(β-carbamoylethyl)-1,2-propylenediamine, and N,N′-bis-(β-carbamoylethyl)-2-hydroxyltrimethylenediamine were determined potentiometrically in 0.10 mol dm?3 NaNO3 at 25.0°C. The formation of Cu(II) complexes of these ligands and the CuO to CuN bond rearrangements at the two amide sites of these complexes were investigated quantitatively by potentiometric and spectrophotometric techniques under the same conditions. Electronic spectra of the Cu(II) complexes of these ligands and their deprotonated species formed in aqueous solution were measured and discussed. 相似文献
7.
A new pentadentate Schiff base 2,6,10-triaza-1,11-bis(2′-aminophenyl)-undeca-1,10-diene, abaDPT, and its complexes of general formula M(abaDPT)X2 where M = Cu(II), Ni(II), X = Cl, Br, I, NO3 and ClO4, have been prepared. The complexes have been characterized by electronic and IR spectra, EPR, magnetic moments, molar conductances, and elemental analysis. IR data show an interaction between halide anion of the outer coordination sphere and the complexed amino group. EPR and spectrophotometric data of most of the copper compounds are consistent with a distorted square pyramidal geometry. Single crystal EPR studies of Cu(abaDPT)(NO3)2 and Cu(abaDPT)Br2 revealed that copper atoms in the former compound occupy two magnetically inequivalent places in the lattice while copper atoms in the latter compound take identical sites. Principal g tensor axes of the two compounds have been determined. 相似文献
8.
A study was made of the reactions between chlorotris(methyldiphenylphosphine)copper(I) and several hydroborates containing a boron-oxygen bond. The new complex ((acetoxy)trihydroborato)tris(methyldiphenylphosphine)copper(I) (Ph2MeP)3CuH3B(O2CCH3) was isolated and characterized by analysis, IR, and NMR data. Analogous reaction conditions using HB(OR)3? anions did not give a BH containing product nor did several other anions of the general type HBR3?. The ability of the hydroborate to complex is related to the Lewis acidity of the respective borane attached to H?. 相似文献
9.
Transition metal complexes with 1,3-bis-(2-hydroxyphenyl)-1,3-propanedione—I : Mononuclear complexes
Reaction of 1,3-(2-hydroxyphenyl)-1,3-propanedione (BhPPH3), a ligand with three possible sites of coordination acting as a chelating agent, with metal acetates results in the formation of mononuclear species M(BhPPH2)2S,S′ (M=Mn, Fe, Co, Ni, Zn; S,S′=CH3OH, C2H5OH or H2O); M′(BhPPH2)2 (M′=Cu, Pd), and M″(BhPPH2)3S,S′ (M″= Fe, Al). The complexes have been studied by 1H-NMR when possible, and IR spectra. The position of the methine proton (=CH-) at 6.88 ppm in Zn(BhPPH2)2S,S′ indicates that BhPPH3 behaves in mononuclear complexes as a common β-diketone. Most of the complexes lose S,S′ molecules on heating but a crystal structure of Zn(BhPPH2)2 · 2C2H5)OH indicates that the C2H5OH molecules are oxygen bonded to the metal centre. 相似文献
10.
The preparation and properties of copper(II) complexes of 4-methoxy-2-(4-methoxy-3-methyl-pyrazol-1-yl)-6-methylpyrimidine, are reported. Complexes of 相似文献
11.
Novel neutral biimidazolate or bibenzimidazolate palladium(II) and platinum(II) complexes of the type M(NN)2(dpe) [M = Pd, Pt; (NN)22? = BiIm2?, BiBzIm2?. dpe = 1,2-bis(diphenylphosphino) ethane] have been obtained by reacting MCl2(dpe) with TI2(NN)2. Complexes M(NN)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(NN)2](dpe) (M = Pd, Pt; H2(NN)2 = H2BiIm, H2BiBzIm) and homobinuclear palladium(II) or platinum(II) cationic complexes of the type [M2{μ - (NN)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
12.
The new heteronuclear arene complexes [(COD)Rh(μ-cbz)AuPPh3]ClO4, [{(COD)Rh}2(μ-cbz)AuPPh3](ClO4)2, [(C5Me5)Rh(μ-cbz)AuPPh3](ClO4)2 and [{C5Me5) Rh}2(μ-cbz)AuPPh3](ClO4)4 (COD = 1,5-cyclooctadiene, cbz = carbazolyl), and the mononuclear arene complexes [(COD)Rh(arene)]ClO4 (arene = tetralin, biphenyl, fluorene, indene, 9,10-dihydroanthracene or carbazole) have been prepared by reaction of the acetone solvated complexes [(COD)Rh(Me2CO)x]ClO4 or [(C5Me5)Rh(Me2CO)3](ClO4)2 with (cbz)AuPPh3 or the appropriate polycyclic arene ligand. 相似文献
13.
The synthesis and electronic and IR spectra of CuL2(NO3)2 and CuL4(NO3)2, where L stands for morpholine, are described. The thermal behaviour of the complexes is also discussed. The solids contain distorted octahedral Cu(II) bonded to morpholine through nitrogen only. In aqueous solutions only the species CuL3(aq)2+ is stable in the concentration range 0.5 < [L] < 2 mol dm?3, its stability constant being log K3 = 14.64 ± 0.15 at 25.00°C and ionic strength 1 mol dm?3; at very high morpholine concentrations, 3.4 < [L] < 6 mol dm?3, evidence is also found for CuL4(aq)2+, the value log K4 = 15.5 being estimated. The aggressiveness of morpholine-H2O2 towards metallic copper is compared with that of ammonia-H2O2, both on thermodynamics and kinetics grounds; experimental results seems to be dominated by kinetics factors. The relevance of these results to water treatment in secondary systems of nuclear power reactors is discussed. 相似文献
14.
Stable, pentacoordinated iridium(I) complexes have been synthesised by the replacement of the chlorine in IrCO(PPh3)2Cl by bidentate chelating ligands such as β-diketones, N-benzoyl-N-phenyl hydroxylamine, salicylaldehyde, 8-hydroxyquinoline, 2-hydroxybenzophenone and 2-hydroxy 4-methoxybenzophenone. Most of them gave stable oxygen adducts IrCO(PPh3)2(L)O2 and all of them underwent oxidative addition with bromine in methylene chloride giving IrCO(PPh3)2(L)Br2. These chelated iridium(I) compounds reacted with liquid sulphur dioxide to produce two types of SO2 insertion products. 相似文献
15.
The reactions of [Rh(CO)2Cl]2 with α-diimines, RN=CR′-CR′=NR (R = c-Hex, C6H5, p-C6H4OH, p-C6H4CH3, p-C6H4OCH3, R′ = H; R = c-Hex, C6H5, p-C6H4OH, p-C6H4OCH3; R′ = Me) in 2:1 Rh/R-dim ratio gave rise to ionic compounds [(CO)2Rh.R-dim(R′,R′)][Rh(CO)2Cl2] which have been characterized by elemental analyses, electrical conductivity, 1H-NMR and electronic and IR spectroscopy. Some of these complexes must involve some kind of metal-metal interaction. The complex [Rh(CO)2Cl.c-Hex-dim(H,H)] has been obtained by reaction of [Rh(CO)2Cl]2 with the c-Hex-dim(H,H) ligand in 1:1 Rh/R-dim ratio. The reactions between [(CO)2Rh.R-dim(H,H)][Rh(CO)2Cl2](R = c-Hex or p-C6H4OCH3) with the dppe ligand have been studied. The known complex RhCl(CO)(PPh3)2 has been isolated from the reaction of [(CO)2Rh.R-dim(H,H)]-[Rh(CO)2Cl2] (R = c-Hex or p-C6H4OCH3) with PPh3 ligand. 相似文献
16.
This paper reports the reaction of Ag2(mnt) and [(NEt4)Ag(mnt)] (mnt2? = maleonitriledithiolate) with PPh3 and 1,2-bis(diphenylphosph 相似文献
17.
New complexes of Re(V) with dithiooxamide and 2-mercaptobenzothiazole with the general formula ReOCl3L2, were prepared starting from potassium perrhenate. The compounds were characterised by chemical analysis, optical spectra and magnetic susceptibilities. 相似文献
18.
The new difunction ligand, 2-amino-1-cyclopentenedithio-carboxylate(L), was prepared and its coordination chemistry examined to gain further insight into the reactivity of “aromatic” dithio type ligands. Reaction with MoCl4py2 and VOSO4, led to the surprising eight coordinate products ML4. The sp2 hybridization of the ring carbon to which the CS2 moiety is bonded apparently yields a pseudo-aromatic effect on the reactivity of this ligand. The physical properties of these new compounds are discussed. 相似文献
19.
The reduction of the title complexes was studied by cyclic voltammetry in aqueous media. It proceeds through a one-electron process generating intermediate copper(I) dipeptide complexes. The copper(I) dipeptide complexes are found to be short-lived and undergo transformations eventually generating Cu0 at the mercury electrode. The unchanged fraction of the copper(I) species is re-oxidised to the copper(II) complexes. The Cu0 generated undergoes a two-electron oxidation at a more anodic potential than the copper(I) complexes. pH-dependence of the title complexes is also investigated by cyclic voltammetry. 相似文献
20.
4-chloro,3-methyl,5-phenylisoxazole copper(II) complexes of the type Cu(L)X2(X = Cl, Br, NO3) and Cu(L)2(ClO4)2 have been prepared and studied by the IR, electronic, paramagnetic resonance spectroscopy and molar conductivity values. The ligand acts as monodentate N-bonded except to the nitrate derivative where this behaves as bridging bidentate. The halide complexes are tetrahedral, while the nitrate and perchlorate derivatives are square planar. 相似文献