Darstellung und Charakterisierung von Halogeno(diethyldithiocarbamato) (triethyl- und triphenylphosphin)palladium(II)-Komplexen

The Complexes [Pd(PEt ₃)₂ dtc]X (1) and Pd(PR ₃)Xdtc (2, 3) (dtc=S₂CNEt ₃;X=Cl, Br, I;R=Et, Ph) have been prepared. Conductivity, susceptibility, UV and IR measurements show that the cations [Pd(PEt ₃)₂ dtc]⁺ of1 and the complexes2, 3 have square-planar structure.

     

Darstellung und Charakterisierung von Halogeno(diethyldithiocarbamato) (triethylphosphin)-nickel(II)-Komplexen

The complexes [Ni(PEt ₃)₂ dtc]X (1) and Ni(PEt ₃)Xdtc (2) (dtc=S₂CNEt ₂,X=Cl, Br, I) have been prepared. As conductivity, susceptibility, UV and IR measurements show, the cations [Ni(PEt ₃)₂ dtc]⁺ of1 and the complexes2 at ambient temperature have square-planar structure. We suppose there might exist an equilibrium for2 between square-planar and tetrahedral configuration.

     

SYNTHESIS AND STRUCTURES OF DICHLOROTETRAKIS-(PHENYLTHIOUREA) CADMIUM(II) AND CATENA-BIS(THIOCYANATE) BIS(PHENYLTHIOUREA)CADMIUM(II)

Abstract

Two new cadmium(II) complexes with phenylthiourea (PTU), namely Cd(PTU)₄Cl₂ (1) and [Cd₂(NCS)₂(μ₂-SCN)₂(PTU)₂(μ₂-PTU)₂] _n (2), have been prepared and characterized structurally by X-ray diffaction. Complex 1 crystallizes in the monoclinic space group C2/c, with a = 27.057(13), b = 8.108(3), c = 16.751(8) Å, β = 114.46°, V = 3345(3) ų, Z = 4. Complex 2 crystallizes in the triclinic space group P-1, with a = 9.336(3), b = 14.686(5), c = 16.911(5) Å, α = 71.36(2), β = 84.31(2), γ = 72.470(10)°, V = 2095.0(12) ų Z = 4. The structural analysis shows that each metal atom in both the mononuclear complex 1 and polynuclear complex 2 is octahedrally coordinated by four sulfur atoms and two chloro ligands or two nitrogen atoms from the thiocyanate groups, respectively. The PTU ligand can serve as either a monodentate ligand or a μ₂-bridging ligand upon coordination to a metal atom.     

Zinc(II) (o-hydroxybenzaldoximates) Complexes with Mono- and Bidentate Ligands

New complexes:Zn(Hsalox)(ox), Zn(Hsalox)(NHPh), Zn(Hsalox)(Hsal) and Zn(Hsalox)₂(1,2-diMeim) have been synthesised as a result of a reaction of Zn(salox) and Zn(Hsalox)₂ (where: salox ^2–=OC₆H₄CHNO^2–, Hsalox ^–=OC₆H₄CHNOH^–) with 8-hydroxyquinoline (Hox), o-aminophenol (NH₂Ph), o-hydroxybenzoic acid (H₂Sal) and 1,2-dimethylimidazole (1,2-diMeim). Chemical, X-ray and thermal analyses of the complexes and their sinters have been carried out. Thermal decomposition pathways have been postulated for the complexes. The mixtures about not definite composition have been obtained as a result of a reaction of zinc(o-hydroxybenzaldoximates) with imidazole(Him) and 4-methylimidazole (4-MeHim). This revised version was published online in August 2006 with corrections to the Cover Date.     

Crystal Structures and Characterizations of Bis(pyrrolidinedithiocarbamato)Cu（Ⅱ） and Zn(Ⅱ） Complexes

The structures of [Cu (S₂CN (CH₂)₄)₂] (1) and [Zn₂(S₂CN‐(CH₂)₄)₄] (2) have been determined by X‐ray crystallography analysis. They are all isomorphous and triclinic, space group of P1^?, with Z = 1. The lattice parameters of compound 1 is: a = 0.63483(2) nm, b = 0.74972(3) nm, c=0.78390(1) mn, α = 75.912(2)°, β = 78.634(2)° and γ = 86.845(2)°; compound 2: a = 0.78707(6) nm, b=0.79823(6) nm, c = 1.23246(9) nm, α = 74.813(2)°, β = 73.048(2)° and γ = 88.036(2)°. The copper atom is located on a crystallographic inversion center and zinc atom lies across centers of symmetry. The Cu(II) ion has a square‐planar geometry while Zn(II) has a distorted tetrahedral geometry. The thermal gravity (TG) data indicate that no structural transitions in the two compounds were abserved and the decomposition products can adsorb gas. Also they all have a high thermal stability.     

Syntheses,crystal structures,and spectral properties of Mn(II) and Co(II) complexes with 3-(p-chlorophenyl)- 4-(p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole

Two new complexes, trans-[MnL₂(NCS)₂] (1) and trans-[CoL₂(H₂O)(EtOH)](ClO₄)₂?·?H₂O (2) with asymmetrical triaryltriazole ligands [L?=?3-(p-chlorophenyl)-4-(p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole], have been synthesized and characterized by elemental analysis, FT-IR, ESI-MS, and single-crystal X-ray diffraction. In the complexes each L adopts a chelating bidentate mode via the nitrogen of pyridyl and triazole. Both complexes have a similar distorted octahedral core with two NCS^? ions in the trans position in 1, while one H₂O and one EtOH are present in the axial sites in 2.     

Rhodium(III), palladium(II) and platinum(II) complexes of Bis(o-aminobenzenesulfonyl)ethylenediamine

New complexes of the formulae K₃[RhL ₃]·2 H₂O, [PdL]·H₂O and [M(LH₂)Cl₂] [whereM = Pd, Pt andLH₂ = bis(o-aminobenzenesulfonyl)ethylenediamine] have been prepared and characterized by conductivity measurements, thermogravimetric analysis, X-ray powder patterns and IR, Ligand Field and¹H-NMR spectroscopy.

---

Rhodium(III), Palladium(II)- und Platin(II)-Komplexe mit Bis(o-aminobenzolosulfonyl)ethylendiamin (Kurze Mitteilung)

Zusammenfassung Neue Komplexe der allgemeinen Formeln K₃[RhL ₃]·2H₂O, [PdL]·H₂O und [M(LH₂)Cl₂] mitM = Pd, Pt undLH₂ = Bis(o-aminobenzolosulfonyl)ethylendiamin wurden dargestellt und mit Konduktionsmessungen, thermogravimetrischen Analysen, Röntgenstrukturanalysen, IR, Ligandfeld- und¹H-NMR-Spektroskopie charakterisiert.

     

Lanthanum(III) and prasedymium(III) complexes with piperazine dithiosemicarbazones

Lanthanum(III) and praseodymium(III) complexes of the type [Ln(L)Cl(H₂O)]₂ (Ln = La(III) or Pr(III); LH₂ = dithiosemicarbazone ligands derived from piperazine dithiosemicarbazide and benzaldehyde, 4-nitrobenzaldehyde, and 2-methoxybenzaldehyde) have been synthesized in methanol in the presence of sodium hydroxide. The complexes have been characterized by elemental analyses, molecular weight, molar conductance, electronic absorption, IR, and ¹H and ¹³C NMR spectral studies. Nephelauxetic ratio, covalency parameter, and bonding parameter for these complexes have also been calculated. Thermal studies of the complexes have been carried out using TG, DTG, and DSC techniques. Kinetic parameters, such as apparent activation energy and order of reaction, were determined by the Coats-Redfern graphical method. The heats of reaction for different reaction steps were calculated from DSC curves. The article was submitted by the authors in English.     

Crystal Structures of (18-Crown-6)-(2-Hydroxyethylammonium) Tetracyanonickelate(Ii) and 10-Amino-Decylammonium Tetracyanonickeltate(II)

Abstract

The crystal structures of the two title tetracyanonickelate(II) salts of organic ammonium ions, (18-crown-6)-(2-hydroxyethylammonium) tetracyanonickelate(II), I, and 10-aminodecylammonium tetracyano nick-elate(II), II, have been analyzed. I crystallizes in the monoclinic space group P2₁/n with a = 10.458(2), b = 8.267(3), c = 24.045(2) Å, β = 94.09(1)°, V = 2074(1) ų, Z = 2, R = 0.061 for 2274 reflections; II is triclinic P ₁ with a = 9.437(3), b = 10.094(3), c = 9.205(3)Å,a = 110.16(2), β = 112.72(3), γ = 69.16(2)°, V = 733.7(5) ų 2=1, R = 0.040 including all the hydrogen atoms refined for 2724 reflections. The square planar tetracyanonickelate(II) anion is in a favourable position to form hydrogen bonds via N with the hydroxyl group in I and the ammonio group in II, respectively.     

Thiosemicarbazone Complexes of Ruthenium(II) and Rhodium(I) Containing Triphenylphosphine

Several new hexa-coordinated ruthenium(II) and penta-coordinated rhodium(I) complexes of the types [RuCl(CO)(PPh ₃ ) ₂ (TSC)], [RuH(CO)(PPh ₃ ) ₂ (TSC)], and [Rh(PPh ₃ ) ₃ (TSC)] (where TSC = anion of thiosemicarbazone Schiff bases) have been prepared by the reactions of [RuHCl(CO)(PPh ₃ ) ₃ ], [RuH ₂ (CO)(PPh ₃ ) ₃ )], and [RhH(PPh ₃ ) ₄ ] with thiosemicarbazones of 2-furaldehyde (H-FTSC), thiophene-2-carboxaldehyde (H-TCTSC), p-anisaldehyde (H-ATSC), piperonaldehyde (H-PTSC), and cyclohexanone (H-CTSC). All the new complexes obtained have been characterized on the basis of elemental analysis, IR, ¹ H NMR, ³¹ P NMR, and electronic spectral data.     

Nickel(II) and copper(II) complexes of 2-acetylpyridine 4 N-(2-methylpyridinyl)-, 4 N-(2-ethylpyridinyl)- and 4 N-methyl(2-ethylpyridinyl) thiosemicarbazones

Summary Ni^II and Cu^II complexes of 2-acetylpyridine ⁴ N-(2-methylpyridinyl)-, ⁴ N-(2-ethylpyridinyl)- and ⁴ N-methyl(2-ethylpyridinyl) thiosemicarbazones (HL4pam, HL4pae, and HL4Mpae, respectively) of general formula [M(HL)X₂] have been isolated from boiling EtOH and characterized by physico-chemical and spectroscopic methods. The growth inhibition activities of the thiosemicarbazones and their complexes were measured against Aspergillus nicer and Paecilomyces variotii.     

Synthesis and characterization of mononuclear bis(aryldiazenido)-molybdenum complexes. Crystal structures of [Mo(NNC6HR-p)2-(acac)2] (R = Me and OMe)

Summary [MoO₂(acac)₂] reacts with two equivalents of arylhydrazines in MeOH or MeCN to give mononuclear bis(aryldiazenido) molybdenum complexes of the type [Mo-(NNC₆H₄R-p)₂(acac)₂], where R = H (1); Me (2); MeO (3); F (4) or NO₂ (5). These complexes have been characterized by i.r., ¹H-n.m.r. and u.v.-vis. spectroscopy. The crystal structures of (2) and (3) have been determined. Both lattices are made of discrete mononuclear species containing the cis-[Mo(NNAr)₂]²⁺ unit with singly bent aryldiazenido ligands.     

Synthesis,Crystal Structure and Properties of [Mn(hdpa)2(N(CN)2)2] and [Co(hdpa)2(N(CN)2)2] (hdpa = 2, 2'‐Dipyridylamine)

Two new transition metal(II) complexes [M(hdpa)₂(N(CN)₂)₂] (M = Mn ( 1 ), Co ( 2 ); hdpa = 2, 2'‐dipyridylamine) have been prepared and characterized structurally and magnetically. Both compounds crystallize in the monoclinic space group C2/c. 1 and 2 are isotypic with the unit cell parameters a = 8.634(9), b = 13.541(14), c = 21.99(2) Å, β = 94.806(18)°, and V = 2562(5) ų for 1 , a = 8.617(3) Å, b = 13.629(5)Å, c = 21.598(8)Å, β = 94.593(6)°, and V = 2528.4(15)ų for 2 , and Z = 4 for both. According to X‐ray crystallographic studies, each metal(II) ion was six‐coordinated with four nitrogen atoms from two bidentate hdpa ligand and two nitrogen atoms from two N(CN)^— anions to form slightly distorted octahedrons. Adjacent complex molecules are connected by hydrogen bonds or π···π interactions to form three‐dimensional network. The IR and UV spectroscopy were measured and the magnetic behaviors were investigated.     

Cadmium(II), manganese(II) and zinc(II) compounds

Three new compounds, [Cd(μ ₃ -Hpdh)(μ₂-Cl)] _n (1), Mn(Hpdh)₂(H₂O)₂ (2) and Zn(Hpdh)₂ (H₂O)₂ (3) (H₂pdh =?pyridine-2,3-dicarbo-2,3-hydrazide), have been synthesized and characterized by elemental analysis, IR spectra, TG and single-crystal X-ray diffraction. Under hydrothermal conditions, H₂pdh is generated by an in situ acylation of H₂pda (H₂pda =?pyridine-2,3-dicarboxylic acid) with hydrazine hydrate. Complex 1 features a 2D layer structure constructed by a dinuclear Cd(II) building block. In complexes 2 and 3, hydrogen bonding interactions connect mononuclear structures into 3D supramolecular frameworks.     

Monooxorhenium(V) complexes with the tridentate Schiff baseN-(2-hydroxyphenyl)salicylideneimine

Summary The reactions of the tridentate Schiff base ligandN-(2-hydroxyphenyl) salicylideneimine (HOPhsalH) with oxotetrachlororhenate (IV) have been investigated. The complexes (Bu₄N)[ReOCl₃(HOPhsal)], (Bu₄N)[ReOCl₂(OPhsal)],cis- [ReOCl(MeOH)(OPhsal)],trans-[ReOCl(MeOH)(OPhsal)] (1), trans-[ReOCl(OH₂)(OPhsal)] · Et₂O (2), trans-[ReOCl(OH₂)(OPhsal)] · Me₂CO,cis-[ReOCl(PPh₃)(OPhsal)],cis-[ReOCl(PMe₂Ph)(OPhsal)](3) have been synthesized and characterized. The crystal structures of(1), (2) and(3) have been solved from three-dimensional x-ray data by Patterson and Fourier methods and refined by least-squares methods to R 0.10 for(1), 0.042 for(2) and 0.059 for(3). In all the three complexes, the ligands surrounding the rhenium atom are at the apices of a distorted octahedron, with the equatorial ONO donor atoms of the tridentate Schiff base bent away from the O_oxo and toward the loosely bound MeOH in(1), H₂O in(2) and Cl in(t3). The fourth equatorial substituent is Cl (1 and2) and PMe₂Ph(3) and the rhenium atoms lie 0.30–0.37 Å above the best plane through the four equatorial atoms, in the direction of the O_oxo. All interatomic distances and angles are normal.     

Hexaaquacobalt(II) bis(hypophosphite) and hexaaquacobalt(II)/nickel(II) bis(hypophosphite)

The title compounds, hexa­aqua­cobalt(II) bis­(hypophosphite), [Co(H₂O)₆](H₂­PO₂)₂, and hexa­aqua­cobalt(II)/nickel(II) bis(hypophosphite), [Co_0.5Ni_0.5(H₂O)₆](H₂PO₂)₂, are shown to adopt the same structure as hexa­aqua­magnesium(II) bis­(hypophosphite). The packing of the Co(Ni) and P atoms is the same as in the structure of CaF₂. The Co^II(Ni^II) atoms have a pseudo‐face‐centred cubic cell, with a = b～ 10.3 Å, and the P atoms occupy the tetrahedral cavities. The central metal cation has a slightly distorted octahedral coordination sphere. The geometry of the hypophosphite anion in the structure is very close to ideal, with point symmetry mm2. Each O atom of the hypophosphite anion is hydrogen bonded to three water mol­ecules from different cation complexes, and each H atom of the hypophosphite anion is surrounded by three water mol­ecules from further different cation complexes.     

Complexes of substituted dipyridylpyridazines with palladium(II) and platinum(II)

Reactions of 3,6-bis(2′-pyridyl)pyridazine derivatives (n-dppn)¶ ¶For the n-dppn ligands, n stands for the size of the cyclic aliphatic ring on positions 4 and 5 of the pyridazine ring, n?=?5, 6, 8, and 12. with MX₂(PhCN)₂ (M?=?Pd, Pt; X?=?Cl,?Br) have been investigated. The new complexes cis-[PdCl₂(n-dppn)] (n?=?5,?6,?8,?12), cis-[PtCl₂(n-dppn)]?·?H₂O (n?=?5,?6), cis-[PtCl₂(8-dppn)] and cis-[PtBr₂(5-dppn)] have been characterized by elemental analyses, conductivity measurements, infrared, electronic and ¹H-NMR spectra.     

Reactions of dichloro-bis(cyclopentadienyl)titanium(IV) with bidentate Schiff bases

A series of Cp₂Ti(SB)Cl complexes, whereSB is the anion of bidentate Schiff bases derived from salicylaldehyde and different primary aminesviz o-anisidine,m-anisidine,o-phenetidine,o-chloroaniline,m-chloroaniline,m-nitroaniline, α-naphthylamine and benzylamine, have been synthesised by the reaction of dichloro-bis(cyclopentadienyl) titanium(IV), Cp₂TiCl₂, and bidentate Schiff base (sbh) in a 1:1 molar ratio in refluxingthf in the presence of triethylamine. The new derivatives have been characterised on the basis of their elemental analyses, conductance measurements and spectral (IR,¹Hnmr and electronic) studies     

Structural Isomers of Bis(diphenylarsino)methane‐dichloroplatinum(II)

From a range of preparative methods, three geometric isomers of bis(diphenylarsino)methane‐dichloroplatinum(II) have been isolated, viz. cis‐PtCl₂(dpam), trans, trans‐Pt₂Cl₄(dpam)₂ and cis, trans‐Pt₂Cl₄(dpam)₂. Their structures were determined by single‐crystal X‐ray diffraction.     

SYNTHESES AND CRYSTAL STRUCTURES OF ISOMALONONITRILE DITHIOLATO COMPLEXES (Bu4N)2Zn(i-mnt)2 AND (Et4N)2Pd(i-mnt)2

Abstract

Two isomalononitrile dithiolato complexes, (Bu₄N)₂Zn(i-mnt)₂ (1) and (Et₄N)₂Pd(i-mnt)₂ (2) were synthesized and characterized by elemental analysis, IR and electronic spectroscopy. Their structures have been crystallographically determined. The reaction of (Et₄N)₂Pd(i-mnt)₂ (2) with (Et₄N)₂WS₄ gives (Et₄N)₂WS₄Pd(i-mnt).