Metallic complexes with furan oximes. Part 5 - synthesis and characterization of 5-nitro-2-furfuraldoxime complexes with 3d element dihalides

Summary Following our investigations into the complexing properties of 5-substituted 2-furfuraldoximes, we describe here the first complexes obtained from 5-nitro-2-furfuraldoxime (5-NO₂-FDH or L) and 3d element dihalides, formulated as [ML₂X₂], [ML₃X₂] and [ML₄X₂] (M = Co, Ni or Cu; X = Cl or Br). The structures are discussed on the basis of analytical, i.r. spectral data and thermal analysis.     

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.     

Complexes of Some 3d-Metal Salts with N,N-Dimethylhydrazide of 4-Nitrobenzoic Acid

The [M(HL)₂(H₂O)₂]X₂ complexes were synthesized (M = Mn(II), Co(II), Ni(II), Cu(II), Zn; X = CH₃COO^–, Cl^–, BF₄ ^–) that incorporate bidentately coordinated molecules of N,N-dimethylhydrazide of 4-nitrobenzoic acid (HL). The latter molecules chelate the metal atom through the carbonyl O atom and the N atom of dimethylamino group. The square-planar complexes of Cu and Ni with deprotonated form of a ligand with composition ML₂ were also isolated. The synthesized complexes were studied by IR, electronic and EPR spectroscopies, and by cyclic voltammetry.     

Photochemical reactions of metal carbonyls [M(CO)6 (M = Cr,Mo and W), Re(CO)5Br,Mn(CO)3Cp] with 2-hydroxyacetophenone methanesulfonylhydrazone (apmsh)

Five new complexes, [M(CO)₅(apmsh)] [M = Cr; (1), Mo; (2), W; (3)], [Re(CO)₄Br(apmsh)] (4) and [Mn(CO)₃(apmsh)] (5) have been synthesized by the photochemical reaction of metal carbonyls [M(CO)₆] (M = Cr, Mo and W), [Re(CO)₅Br], and [Mn(CO)₃Cp] with 2-hydroxyacetophenone methanesulfonylhydrazone (apmsh). The complexes have been characterized by elemental analysis, mass spectrometry, f.t.-i.r. and ¹H spectroscopy. Spectroscopic studies show that apmsh behaves as a monodentate ligand coordinating via the imine N donor atom in [M(CO)₅(apmsh)] (1–4) and as a tridentate ligand in (5).     

Novel Copper(I) Clusters with 2‐(Diphenylphosphanyl)anilide Ligands. Synthesis and Crystal Structures of [Cu6X2(NHR)4] (X = Cl,Br, I; R = C6H4‐2‐PPh2)

Treatment of copper(I) halides CuX (X = Cl, Br, I) with lithium 2‐(diphenylphosphanyl)anilide [Li(HL)] in THF led to the formation of hexanuclear copper(I) complexes [Cu₆X₂(HL)₄] [X = Cl ( 1 ), Br ( 2 ), I ( 3 )]. In compounds 1 – 3 , the copper atoms are in a distorted octahedral arrangement and the amide ligands adopt a μ₃‐κP,κ²N bridging mode. Additionally there are two μ₂‐bridging halide ligands. Each of the [Cu₆X₂(HL)₄] clusters comprises two copper atoms, which are surrounded by two amide nitrogen atoms in an almost linear coordination [Cu–N: 186.2(3)–188.0(3) pm] and four copper atoms, which are connected to an amide N atom, a P atom, and a halogen atom in a distorted trigonal planar fashion [Cu–N: 199.6(3)–202.3(3) pm)].     

The coordination chemistry ofN,N′-ethylenebis(2-acetylpyridine imine) andN,N′-ethylenebis(2-benzoylpyridine imine); two potentially tetradentate ligands containing four nitrogen atoms

Summary New complexes of the general formulae [ML_A(H₂O)₂]-Cl₂ (M=Ni or Cu), [ML_AX₂] (M=Co or Cu; X=Cl or Br), [NiL_ABr₂]·H₂O, [ML_A] [MCl₄] (M=Pd or Pt), [NiL_B(H₂O)₂]Cl₂·2H₂O, [ML_BCl₂] (M=Co, Ni, Cu, Pd or Pt; X=Cl or Br) and [ML_B] [MCl₄] (M=Pd or Pt), where L_A=N,N-ethylenebis(2-acetylpyridine imine) and L_B=N, N-ethylenebis(2-benzoylpyridine imine), have been isolated. The complexes were characterized by elemental analyses, conductivity measurements, t.g./d.t.g. methods, magnetic susceptibilities and spectroscopic (i.r., far-i.r., ligand field,¹Hn.m.r.) studies. Monomeric pseudo-octahedral stereochemistries for the Co^II, Ni^II and Cu^II complexes andcis square planar structures for the compounds [ML_BX₂] (M=Pd or Pt; X=Cl or Br) are assigned in the solid state. The molecules L_A and L_B behave as tetradentate chelate ligands in the Co^II, Ni^II, Cu^II and Magnus-type Pd^II and Pt^II complexes, bonding through both the pyridine and methine nitrogen atoms. A bidentateN-methine coordination of the Schiff base L_B is assigned in the [ML_BX₂] complexes (M=Pd or Pt; X=Cl or Br). The anomalous magnetic moment values of the Co^II complexes are discussed.     

Novel ‘quinolone’ metal complexes: Synthesis and spectroscopic studies of mg(II), zn(II) and ba(II) complexes with N‐methyl (or NH)‐3‐acetyl‐4‐hydroxy quinolin‐2‐one ligands

The complexation between N‐methyl‐3‐acetyl‐4‐hydroxyquinolin‐2‐one (NMeQuin) and N‐H‐3‐acetyl‐4‐hydroxy quinolin‐2‐one (NHQuin) with MgCl₂, ZnCl₂ and BaCl₂ has been accomplished. The structure of the resulting complexes 1–5 has been elucidated through elemental analyses, FT‐IR and ¹H/¹³C NMR Spectroscopy and Mass Spectrometry. The spectroscopic data show complexes of the general formula Mg₂(OH)L₃(H₂O)_z and ML₂(H₂O)_Z where: M = Zn(II) and Ba(II), L = NMeQuin, NHQuin and z = 2, 4.     

Complexes of aminobenzylamines. part II. Complexes ofo-aminobenzylamine with palladium(II) and platinum(II)

Summary The reactions of K₂[MX₄] (M = Pd^II or Pt^II and X = Cl or Br) witho-aminobenzylamine (o-aba) have been studied in neutral aqueous solutions. Two types of complexes were isolated from these studies: [MLX₂] and [ML₂]X₂. Elemental analyses, conductivity measurements, i.r. and visible spectra suggest polymeric structures for [MLX₂] with the ligand,o-aba = L, acting as a bridge, and/or mononuclear structures for [ML₂]X₂.     

Nickel(II) and cobalt(II) coordination compounds of dichloroguanidinopyrimidines

Summary New coordination compounds of Ni^II and Co^II with dichloropyrimidinoguanidine (L) have been obtained and characterized by physico-chemical and spectroscopic methods. The complexes have the general formulae: [ML₃](ClO₄)₂, [ML₂(SO₄)], [ML₂(NCS)₂], (M = Ni or Co), [NiL₂(ClO₄)₂] and [CoL₂](ClO₄)₂. The ligands are bonded to the metal ion via one nitrogen atom from the pyrimidine heterocyclic ring and one from the guanidine group.     

3d-Metal nitroprusside-4-phenylthiosemicarbazide complexes: Synthesis and properties

3d-Metal nitroprusside complexes with 4-phenylthiosemicarbazide of the composition [ML₂][Fe(CN)₅NO] and [CoL₃]₂[Fe(CN)₅NO]₃(M = Ni, Cu, Zn; L = 4-phenylthiosemicarbazide) are synthesized and their structures and physicochemical properties are studied by IR and diffuse reflection spectroscopy and DTA.     

Synthesis, characterization, and biological activities of some transition metal(II) complexes with the thiosemicarbazone derived from 4-[1-(4-methylphenylsulfonyl)-1H-indol-3-yl]but-3-en-2-one

A new 4-[1-(4-methylphenylsulfonyl)-1H-indol-3-yl]but-3-en-2-one thiosemicarbazone (HL) was synthesized derived from 4-[1-(4-methylphenylsulfonyl)-1H-indol-3-yl]but-3-en-2-one. Four transition metal(II) complexes of HL have been prepared. Elemental analysis, molar conductivity, IR, UV, ¹H NMR spectra, and TG-DTA have been used to characterize these complexes. The complexes have the general formula ML₂, where M = Zn, Cu, Co, and Ni. The ligand and its complexes have been studied for their possible biological activity including anti-inflammatory, antibacterial, and antitumour activity in vitro.     

Synthesis,Structure and Properties of Some 3d-Element Complexes with 2-[2-(Hydroxybenzylidene)-amino]-2-hydoxymethylpropane-1,3-diol

2-[2-(Hydroxybenzylidene)-amino]-2-hydoxymethylpropane-1,3-diol (HL) reacts with cobalt, nickel, copper and zinc chlorides, bromides and acetates in water–ethanol solutions and gives MLX · nH₂O and ML₂ · nH₂O complexes (M = Co, Ni, Cu, Zn; X = Cl, Br; n = 0–5). Single crystals of CuLBr were grown, and its crystal structure was determined by X-ray diffraction analysis. The crystals are tetragonal, a = 17.024(2), c = 8.720(2) Å, space group P 2₁ c, Z = 8, R ₁ = 0.0349. In the structure of this complex, the copper atom coordinates the deprotonated HL molecule. The coordination polyhedron of the central atom is an elongated tetragonal pyramid. Its base is built of the imine nitrogen atom, phenolic and alcoholic oxygen atoms, and bromine atom. The apex of the pyramid is occupied by the bromine atom of the adjacent complex connected with the initial complex by the plane of sliding reflection. Thus, the crystal contains infinite chains of complexes running along the c axis, the complexes being united by both bridging bromine atoms and O–H···O hydrogen bonds. The conclusions on the compositions and structures of the remaining compounds were made on the basis of elemental and combined thermal analyses, IR spectroscopy, and magnetic chemistry data. The copper halide complexes were found to have dimeric, and the other metal complexes monomeric, structures. In the synthesized complexes, the azomethine HL can function as a bidentate or tridentate ligand. The thermolysis of the coordination compounds proceeds through the stages of elimination of crystal water molecules (75–90°C) or inner-sphere water molecules (145–155°C) and complete thermal destruction (485–550°C).     

Complex compounds of 1,5-disubstituted 2,4-dithiobiurets with zinc(II) and cadmium(II) chloride

Anhydrous ZnCl₂ and CdCl₂ react with 1,5-disubstituted 2,4-dithiobiurets to give complexes of general formula [ML₂]Cl₂. The complexes have been characterized on the basis of conductance, magnetic and i.r. spectral studies. Co-ordination through sulphur atom and tetrahedral configuration have been proposed for these complexes.     

Palladium(II) and platinum(II) complexes of rhodanine and 3-methylrhodanine

Summary The following palladium(II) and platinum(ll) complexes of rhodanine (HRd) and 3-methylrhodanine (MRd) have been prepared: Pd(HRd)_1.5Cl₂, Pd(HRd)₂Br₂, Pd(HRd)₂Br₂ · 0.25 EtOH, M(MRd)₂X₂ [M = Pd, X = Cl (0.25 EtOH) or Br; M = Pt, X = Cl or Br], Pd(MRd)₃Br₂, and M(MRd)₄(ClO₄)₂ (M = Pd or Pt). The ligands are coordinated to the metal through the thiocarbonylic sulphur atom. Pd(HRd)_1.5Cl₂ has presumably a structure such as (X = Cl or Br) complexes have a trans-planar coordination. Pd(MRd)₂X₂ (X = Cl or Br) complexes arecis-planar coordinated. Pd(MRd)₃Br₂ has presumably a square coordination with two MRd molecules and two CI ionscis-coordinated in the equatorial plane, and a MRd molecule and a Cl ion weakly bonded in apical position. The M(MRd)₄(ClO₄)₂ complexes have square planar coordination.Author to whom all correspondence should be addressed.     

Monohaloboryls (BHX−) as Bridging Ligands: Observable Dinuclear σ‐(Halo)boranyl Intermediates in the Synthesis of Metalloborylenes

Upon treating transition‐metal–dihaloboryl complexes of the form [L_nMBX₂] with K[(η⁵‐C₅H₅)MnH(CO)₂], salt elimination occurs along with a migration of the Mn‐bound hydride ligand onto the boron atom, thereby forming dinuclear σ‐(halo)boranyl complexes of the form [L_nM(μ‐BHX)Mn(CO)₂(η⁵‐C₅H₅)]. Most of these complexes react further at room temperature to lose HX and provide metalloborylene complexes [L_nM‐B=Mn(CO)₂(η⁵‐C₅H₅)]; however, when ML_n=Re(CO)₅ the σ‐(halo)boranyl complex decomposes into unidentifiable products. We found through DFT calculations that two electronically and structurally distinct forms of the intermediate σ‐(halo)boranyl complexes exist, one of which easily loses HX and one that does not.     

Metal complexes of pyrimidine-derived ligands — Part 6. Bischelates of cobalt(II), nickel(II) and monochelates of copper(II) with 3, 5-dimethyl-1-(4′, 6′-dimethyl-2′-pyrimidyl)pyrazole,a potential antitumour agent

Summary Cobalt(II), nickel(II) and copper(II) complexes of 3, 5-dimethyl-1-(4, 6-dimethyl-2-pyrimidyl)pyrazole (DPymPz) have been synthesized and characterized. Magnetic and electronic spectral features show that both [M(DPymPz)₂X₂]·nH₂O [M=cobalt(II) or nickel(II), X=Cl, Br, I, SCN, NO₃, ClO₄ or BF₄ andn=0 or 2] and [Cu(DPymPz)X₂(H₂O)₂] (X=Cl, Br or SCN) are essentially octahedral species. The i.r. spectra indicate that DPymPz is a neutral bidentate ligand being the pyrazolyl and one pyrimidyl ring nitrogen. The X is bonded to the central metal ion in a majority of the complexes.Part 5: N. Saha and D. Mukherjee,Polyhedron,5, 1317 (1986).     

Nickel(II) and copper(II) complexes of ONS ligands formed from 2-hydroxyacetophenone and S-alkyldithiocarbazates and the X-ray crystal structure of the [Ni(Ap-SMe)py] complex (Ap-SMe = anion of the 2-hydroxyacetophenone Schiff base of S-methyl-dithiocarbazate)

Summary New nickel(II) and copper(II) complexes of general formulae [M(Ap-SR)] and [Ap-SR)B] (Ap-SR = dianionic forms of the Schiff bases of 2-hydroxyacetophenone and S-alkyl esters of dithiocarbazic acid; M = Ni^II or Cu^II; R = Me or CH₂Ph; B = py, phen or dipy have been synthesized and characterized by a variety of physicochemical techniques. Magnetic and spectroscopic data support an oxygen-bridged binuclear structure for the [M(Ap-SR)] complexes. The [M(Ap-SR)py] complexes are four-coordinate and square planar, whereas the [M(Ap-SR)B] complexes (B = phen or dipy) are five-coordinate and probably trigonal bipyramidal. The [Cu(Ap-SR)B] complexes (B = py, phen or dipy) obey the Curie-Weiss law over the 298-93 K range.The structure of the [Ni(Ap-SMe)py] complex has been determined by X-ray crystallography. It has an approximately square-planar structure in which the doubly-deprotonated Schiff base is coordinated to the Ni^II ion via the azomethine N atom, the phenolic O atom and the thiolato S atom. The fourth coordination position around the Ni^II ion is occupied by the N of the pyridine ligand.     

Synthesis and characterization of cobalt(II), nickel(II), copper(II) and zinc(II) complexes with acetylacetone bis-benzoylhydrazone and acetylacetone bis-isonicotinoylhydrazone

Summary Acetylacetone bis-benzoylhydrazone (PhCONHN=CMe)₂ CH₂(LH₂) and acetylacetone bis-isonicotinoylhydrazone (NC₅H₄CONHN=CMe)₂CH₂(LH₂) complexes of the types [ML] and [ML] (M = Co^II, Ni^II, Cu^II or Zn^II) have been prepared and characterized. All the complexes are non-electrolytes and the cobalt(II) complexes are lowspin, the nickel(II) complexes are diamagnetic and the copper(II) complexes are paramagnetic. The ligands chelate via two C=N groups and two deprotonated enolate groups. The e.s.r. spectra of the copper(II) complexes indicate a tetragonally distorted dimeric structure. The X-ray diffraction parameters for [CoL] and [NiL] correspond to a tetragonal crystal lattice.     

Co(II), Ni(II) and Cu(II) Complexes with 1-(4-Hydroxyphenyl)-1H-1,2,4-Triazole

New complexes of Co(II), Ni(II), and Cu(II) with 1-(4-hydroxyphenyl)-1H-1,2,4-triazole (L) of the composition ML₂(H₂O)₂(NO₃)₂ · nH₂O (M = Co(II), n = 3; M = Ni(II), n = 0; M = Cu(II), n = 0) were synthesized and studied by photoelectron and IR spectroscopy, magnetochemistry, thermogravimetry, and X-ray powder diffraction analysis. The type of _eff(T) relationship suggests that paramagnetic centers in the Co(II) chloride and Cu(II) nitrate and bromide complexes are involved in antiferromagnetic exchange interactions. The exchange energy values were estimated by the molecular field method.     

Complexes of 2-(2-hydroxyacetophenone)imino-5-(p-anisyl)-1,3,4-oxadiazole with some bivalent metals ions

Summary The metal complexes of the type [M(SB)₂(H₂O)₂] and [M(SB)₂][where M = Mn^II, Co^II, Ni^II or Cu^II, M = Zn^II Cd^II, Hg^II and Pb^II and SBH = 2-(2-hydroxyacetophenone)imino-5-(p-anisyl)-1,3,4-oxadiazole] have been prepared and characterised by elemental analyses, thermal analyses, magnetic measurements, electronic and infrared spectral studies. The complexes [M(SB)₂(H₂O)₂] possess octahedral structures, whereas complexes [M(SB)₂] are tetrahedral. The crystal field parameters of the Co^II and Ni^II complexes are also calculated.