Synthesis of 5-acetyl-4,6-dimethyl-1,2,3,4-tetrahydropyrimidine-2-thione and structural characterization of its polymorphs and complexes with 12-group metal iodides

A novel cyclic thiourea, 5-acetyl-4,6-dimethyl-1,2,3,4-tetrahydropyrimidine-2-thione (L), was synthesized by the reaction of N-(1-tosylethyl)thiourea with potassium enolate of acetylacetone followed by acid-catalyzed dehydration of the obtained 5-acetyl-4-hydroxy-4,6-dimethylhexahydropyrimidine-2-thione. Its polymorphs and complexes with zinc, cadmium, and mercury iodides were studied by X-ray diffraction. Two polymorphs of 5-acetyl-4,6-dimethyl-1,2,3,4-tetrahydropyrimidine-2-thione differ in ring conformation and packing manner. In the monomeric cadmium complex [CdL₂I₂], the central atom is tetrahedrally coordinated in the standard manner by iodine and thiocarbonyl S atoms, while in the dimeric mercury complex [Hg₂L₂I₄], every mercury atom is coordinated by two bridging I atoms, one terminal I atom and one thiocarbonyl S atom of the ligand. In the polymeric zinc complex [ZnLI₂], the zinc tetrahedra are linked by the bidentate bridging 5-acetyl-4,6-dimethyl-1,2,3,4-tetrahydropyrimidine-2-thione molecules through thiocarbonyl S atom and acetyl O atom.     

1,2-Bis-[(5-methyl/chloro/nitro)-2-1H-benzimidazolyl]-1,2-ethanediols and their PdCl2 complexes

1,2-Bis-[(5-methyl)-2-1H-benzimidazolyl]- (L ¹), 1,2-bis-[(5-chloro)-2-1H-benzimidazolyl]- (L ²), 1,2-bis-[(5-nitro)-2-1H-benzimidazolyl]-1,2-ethanediol (L ³) and their PdCl₂ complexes were synthesized and characterized by elemental analysis, molar conductivity, i.r. and ¹H-n.m.r. spectra. The benzene ring substituents lead to a decrease in melting point. The methyl group reduces the solubility and the acidity of L ¹ and Pd(L ¹)Cl₂, whereas the Cl and NO₂ groups increase the solubility and the acidity of L ², L ³, Pd(L ²)Cl₂ and Pd(L ³)Cl₂. In Pd(L ¹)Cl₂ and Pd(L ²)Cl₂ complexes, the ligands act as a bidentate through two nitrogen atoms. In Pd(L ³)Cl₂, ligand coordination occurs through one OH group oxygen atom and one of the benzimidazole nitrogen atoms.     

Copper(II) and palladium(II) complexes of 2-amino-5-chlorobenzophenone and 2-(2-hydroxybenzylidene)amino-5-chlorobenzophenone-<Emphasis Type="Italic">S</Emphasis>-methyl-thiosemicarbazones

The S-methyl thiosemicarbazone derivatives of 2-amino-5-chlorobenzophenone and 2-(2-hydroxybenzylidene)amino-5-chlorobenzophenone (L^I and L^II) and their copper(II) and palladium(II) chelates were synthesized. The solid compounds, [Cu(L^I)Cl]Cl · 2H₂O, [Cu(L^II)Cl]Cl · H₂O, [Pd(L^I)Cl]Cl, and [Pd(L^II)Cl₂], were characterized by elemental analysis, thermogravimetric measurements, electronic, i.r., ¹H-n.m.r. and e.p.r. spectroscopy. The ligand behavior of the L^I and L^II explained by means of spectroscopic data. The experimental X-band e.p.r. spectra recorded from two different copper(II) ion coordinated powder complexes have characteristic line shapes that exhibit the axial symmetry around the paramagnetic ions. The theoretically well fitted spectra prove this case too. The absence of hyperfine signals has been attributed to the strong covalency effects of copper electrons with neighbouring N atoms. Orbital energy levels for magnetic electrons were determined from Spin Hamiltonian parameters. The anisotropic Lande splitting factors were specified in an order of and this case indicates that the unpaired electrons are located mainly in the orbital.     

Platinum(II) and palladium(II) chlorides complexes with purine,pyrimidine,N-ethylimidazole andN-propylimidazole

Summary Platinum(II) and palladium(II) chloride complexes with purine, pyrimidine (pyrimid),N-ethylimidazole(N-EtIm) andN-propylimidazole(N-PropIm) ligands have been prepared and characterized by analysis and spectroscopic methods. The compounds have general formula M(L₁)(L₂)Cl₂ where M=Pt^II, Pd^II; L₁=purine or pyrimid, L₂=N-EtIm orN-PropIm, except the complexes Pt(purine)(pyrimid)Cl₂ and [Pd(purine)(pyrimid)₂Cl]Cl and [Pt(purine)₂ (N-propIm)Cl]Cl·2H₂O.     

Co(II), Ni(II), and Cu(II) Complexation with Isatin Aminoguanisone and Nitroaminoguanisone

New complexes of bivalent Co, Ni, and Cu with isatin aminoguanisone (HL) and nitroaminoguanisone (HL¹) of the composition ([Co(HL)₂]Cl₂ (I), [Ni(HL)₂]Cl₂ (II), [Cu(L)Cl] (III), [Co(L¹)₂] (IV), [Ni(L¹)₂] (V), and [Cu(L¹)₂] (VI) are synthesized. Their molecular conductivities and effective magnetic moments are measured and thermal stabilities are studied. The type of the ligand coordination in I–VI is proposed on the basis of IR data. The summary of physicochemical data for I–VI and the energy calculations for their molecules by the molecular mechanics method made it possible to establish stoichiometry of the coordination polyhedra of the complexes.     

Synthesis,spectroscopic, thermal,and antimicrobial studies of tetradentate 12 and 14 member Schiff bases and their complexes with Fe(III), Co(II), and Cu(II)

Two Schiff bases, L¹ (5,6;11,12-dibenzophenone-2,3,8,9-tetramethyl-1,4,7,10-tetraazacyclododeca-1,3,7,9-tetraene) and L² (6,7;13,14-dibenzophenone-2,4,9,11-tetramethyl-1,5,8,12-tetraazacyclotetradeca-1,4,8,11-tetraene), bearing functionalized pendant arms have been synthesized by cyclocondensation of 3,4-diaminobenzophenone with 2,3-butanedione and 2,4-pentanedione, respectively. Mononuclear macrocyclic complexes [FeL¹Cl₂]Cl, [FeL²Cl₂]Cl, [ML¹Cl₂], and [ML²Cl₂] (where M?=?Co(II) and Cu(II)) have been prepared by reacting iron(III), cobalt(II), and copper(II) with the preformed Schiff base. The ligands and their corresponding metal complexes were characterized by elemental analyses, ESI-mass spectra, conductivity, magnetic moments, UV-Vis, EPR, IR, ¹H-, and ¹³C-NMR spectral studies, and TGA-DTA/DSC data. The TGA profiles exhibit a two-step pyrolysis, although the iron complexes decompose in three steps, leaving behind metal oxides as the final product. The ligands and complexes were screened in vitro against Gram-positive bacteria, Gram-negative bacteria, and fungi.     

Kohlenwasserstoffverbrückte Metallkomplexe. L Dicarbonyl‐cyclopentadienyl‐pyridoyl‐eisen‐Komplexe als Liganden

Hydrocarbon‐bridged Metal Complexes. L Dicarbonyl Cyclopentadienyl Pyridoyl Iron Complexes as Ligands Dicarbonyl‐cyclopentadienyl‐2‐ and 3‐pyridoyl‐iron (L¹, L²) and 2,6‐dicarbonyl‐pyridine‐bis(dicarbonyl‐cyclopentadienyl‐iron) (L³) function as ligands in metal complexes and the N,O‐chelates [(OC)₄M(L¹)] (M = Mo, W, 8 a, b ) and [(Ph₃P)₂Cu(L¹)]⁺BF₄^– ( 9 ) were prepared. Monodentate coordination of L¹ and L² through the pyridine N‐atom occurs in the palladium(II) complexes [Cl₂Pd(PnBu₃)(L¹)] ( 10 ), [Cl₂Pd(PnBu₃)(L²)] ( 11 ) and [Cl₂Pd(L²)₂] ( 12 ). Ligand L³ forms the O,N,O‐bis(chelate) [Cl₂Zn(L³)] ( 13 ). The crystal and molecular structures of L¹, 8 b (M = W), 9–11 and 13 were determined by X‐ray diffraction.     

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.     

Palladium complexes of multidentate pyrazolylmethyl pyridine ligands: Synthesis,structures and phenylacetylene polymerization

The compounds, 2,6-bis(3,5-dimethylpyrazol-1-ylmethyl)pyridine (_MeNˆNˆN) (L1) and 2,6-bis(3,5-ditertbutylpyrazol-1-ylmethyl)pyridine (_tBuNˆNˆN) (L2), react with either [Pd(NCMe)₂Cl₂] or [Pd(COD)ClMe] to form the mononuclear palladium complexes [Pd(_MeNˆNˆN)Cl₂] (1), [Pd(_MeNˆNˆN)ClMe] (2), [Pd(_tBuNˆNˆN)Cl₂] (3) and [Pd(_tBuNˆNˆN)ClMe] (4). Reactions of 1, 2 and 4 with the halide abstractor, NaBAr₄ (Ar = 3,5-(CF₃)₂C₆H₃), led to the formation of stable tridentate cationic species [Pd(_MeNˆNˆN)Cl]⁺(5), [Pd(_MeNˆNˆN)Me]⁺ (6) and [Pd(_tBuNˆNˆN)Cl]⁺ (7) respectively. The analogous carbonyl linker cationic species [Pd{(3,5-Me₂pz-CO)₂-py}Cl]⁺ (9) and [Pd{(3,5-^tBu₂pz-CO)₂-py}Cl]⁺ (10), prepared by halide abstraction of the neutral complexes [Pd{(3,5-Me₂pz-CO)₂-py}Cl₂] and [Pd{(3,5-^tBu₂pz-CO)₂-py}Cl₂] by NaBAr₄, were however less stable with t_1/2 of 14 and 2 days respectively. Attempts to crystallize 1 and 3 from the mother liquor resulted in the isolation of the salts [Pd(_MeNˆNˆN)Cl]₂[Pd₂Cl₆] (11) and [Pd(_tBuNˆNˆN)Cl]₂[Pd₂Cl₆] (12). Although when complexes 1–4 were reacted with modified methylaluminoxane (MMAO) or NaBAr₄, no active catalysts for ethylene oligomerization or polymerization were formed, activation with silver triflate (AgOTf) produced active catalysts that oligomerized and polymerized phenylacetylene to a mixture of cis-transoidal and trans-cisoidal polyphenylacetylene.     

Platinum(IV) and palladium(II) thiosemicarbazide and thiodiamine complexes: A spectral and antibacterial study

Platinum(IV) and palladium(II) complexes [Pt(L)₂Cl₂] and [Pd(L)Cl₂], [where, L?=?1,1-diphenyl-2-thiosemicarbazide (L¹) and (1,1-diphenyl-2-thio)-1,3-propanediamine (L²) have been synthesized. The thiosemicarbazides and thiodiamines exist as the thione-thiol tautomer and coordinate as a bidentate N-S ligand. The ligands are monobasic bidentate. The complexes have been characterized by elemental analysis, IR, mass, electronic and 1H NMR spectroscopic studies. In vitro antibacterial studies have also been carried out for some complexes.     

Triphenylphosphinopalladium(II) complexes with ONO‐donor ligands: syntheses,structures and catalytic applications in C?C cross‐coupling reactions

Reactions of 1‐((2‐hydroxy‐5‐R‐phenylimino)methyl)naphthalen‐2‐ols (H₂Lⁿ , n  = 1–3 for R = H, Me, Cl, respectively) with [Pd(PPh₃)₂Cl₂] and Et₃N in toluene under reflux produced three new mononuclear square‐planar palladium(II) complexes with the general formula [Pd(Lⁿ )(PPh₃)] ( 1 , R = H; 2 , R = Me; 3 , R = Cl). All the complexes were characterized using elemental analysis, solution conductivity and various spectroscopic (infrared, UV–visible and NMR) measurements. Molecular structures of 1 , 2 , 3 were confirmed using single‐crystal X‐ray diffraction analysis. In each complex, the fused 5,6‐membered chelate rings forming phenolate‐O, azomethine‐N and naphtholate‐O donor (Lⁿ )²⁻ and the PPh₃ form a square‐planar ONOP coordination environment around the metal centre. Infrared and NMR spectroscopic features of 1 , 2 , 3 are consistent with their molecular structures. Electronic spectra of the three complexes display several strong primarily ligand‐centred absorption bands in the range 322–476 nm. All the complexes were found to be effective catalysts for carbon–carbon cross‐coupling reactions of arylboronic acids with aromatic and heteroaromatic aldehydes to form the corresponding diaryl ketones. Copyright © 2016 John Wiley & Sons, Ltd.     

Rh(III), Pd(II), Pt(IV) and Au(III) complexes of 2-thiopyrimidine derivatives

Some news thiopyrimidine derivatives and complexes [4-amino-5-nitroso-6-oxo-1,2,3,6-tetrahydro-2-thio-pyrimidine (TANH), its 2-methylthio derivative (MTH), the ammonium salt ofTANH (sTANH) and six new complexes of formulas: Rh(MT)₂Cl · 2H₂O, Pd(MTH)₂Cl₂, Pt(MTH)₂Cl₄, Au(MTH)Cl₃ Pd(TANH)₂Cl₂ and Au(TAN ^–)Cl] have been synthesized and characterized by elemental analysis, IR and¹H-NMR spectroscopy techniques. The thermal behaviour of all compounds has also been studied.

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Rh(III), Pd(II), Pt(IV) und Au(III) Komplexe von 2-Thiopyrimidin Derivaten

Zusammenfassung Es wurden einige neue Thiopyrimidinderivate und deren Komplexe synthetisiert und mittels Elementaranalyse, IR und¹H-NMR charakterisiert: 4-Amino-5-nitroso-6-oxo-1,2,3,6-tetrahydro-2-thio-pyrimidin (TANH), dessen 2-Methylthio-Derivat (MTH), das Ammoniumsalz vonTANH (sTANH) und sechs neue Komplexe der Formeln Rh(MT)₂Cl · 2H₂O, Pd(MTH)₂Cl₂, Pt(MTH)₂Cl₄, Au(MTH)Cl₃, Pd(TANH)₂Cl₂ und Au(TAN ^–)Cl. Das thermische Verhalten der Verbindungen wurde ebenfalls untersucht.

     

Cu(II) and Pd(II) complexes of N-(2-hydroxybenzyl)aminopyridines

N-(2-Hydroxybenzyl)aminopyridines (Lⁱ) react with Cu(II) and Pd(II) ions to form complexes in the compositions Cu(Lⁱ)₂(CH₃COO)₂ · nH₂O (n = 0, 2, 4), Pd(Lⁱ)₂Cl₂ · nC₂H₅OH (n = 0, 2) and Pd(L²)₂Cl₂ · 2H₂O. In the complexes, the ligands are neutral and monodentate which coordinate through pyridinic nitrogen. Crystal data of the complexes obtained from 2-amino pyridine derivative have pointed such a coordinating route and comparison of the spectral data suggests the validity of similar complexation modes of other analog ligands. Cu(II) complex of N-(2-hydroxybenzyl)-2-aminopyridine (L¹), [Cu(L¹)₂(CH₃COO)₂] has slightly distorted square planar cis-mononuclear structure which is built by two oxygen atoms of two monodentate carboxylic groups disposed in cis-position and two nitrogen atoms of two pyridine rings. The remaining two oxygen atoms of two carboxylic groups form two Cu and H bridges containing cycles which joint at same four coordinated copper(II) ion. IR and electronic spectral data and the magnetic moments as well as the thermogravimetric analyses also specify on mononuclear octahedric structure of complexes [Cu(L²)₂(CH₃COO)₂ · 2H₂O] and [Cu(L³)₂(CH₃COO)₂ · 4H₂O] where L² and L³ are N-(2-hydroxybenzyl)-2- or 3-aminopyridines, respectively.     

Synthesis and Structure of Metal Complexes of 1-(1-R-3-Methylpyrazole-5-onilidene-4)-1,2,3,4-tetrahydroisoquinoline Derivatives

Twenty new complexes were synthesized by reacting Co(II), Cu(II), Zn, Cr(III), Fe(III), Cd and Ag salts with 3,3-dimethyl-1-(3-methylpyrazole-5-onilidene-4)-1,2,3,4-tetrahydroisoquinoline (L¹), spiro{cyclohexane-1,3"-[1-(1-phenyl-3-methylpyrazole-5-onilidene-4)-1,2,3,4-tetrahydroisoquinoline]} (L²), and 3,3-dimethyl-1-(1-phenyl-3-methylpyrazole-5-onilidene-4)-1,2,3,4-tetrahydroisoquinoline (L³). These compounds were studied by IR and electronic absorption spectroscopy. The type of coordination of their ligands was discussed on the basis of the results obtained and X-ray diffraction data for L³ and [CuL₂ ² Cl₂] · 2L² obtained previously.     

1-Selenolato-2-phenyl-o-carborane complexes of palladium(II) and platinum(II): Synthesis, spectroscopy and structures

The reactions of PhCb^oSeNa (Cb^o = o-C₂B₁₀H₁₀), prepared by reductive cleavage of Se-Se bond in (PhCb^oSe)₂ by NaBH₄ in methanol, with Na₂PdCl₄, MCl₂(PR₃)₂ and [M₂Cl₂(μ-Cl)₂(PR₃)₂] afforded a variety of complexes, viz., [Pd(SeCb^oPh)Cl] (1), [M(SeCb^oPh)₂(PR₃)₂], [M₂Cl₂(μ-SeCb^oPh)(μ-Cl)(PR₃)₂] (M = Pd, Pt) and [Pd₂Cl(SeCb⁰Ph)(μ-Cl)(μ-SeCb^oPh)(PEt₃)₂] (7) have been isolated. These complexes were characterized by elemental analyses and NMR (¹H, ³¹P, ⁷⁷Se, ¹⁹⁵Pt) spectroscopy. The structures of [Pd(SeCb^oPh)₂(PEt₃)₂] (2), [Pt(SeCb^oPh)₂(PMe₂Ph)₂] (3), [Pd₂Cl₂(μ-SeCb^oPh)(μ-Cl)(PMe₂Ph)₂] (5) and [Pd₂Cl(SeCb^oPh)(μ-Cl)(μ-SeCb^oPh)(PEt₃)₂] (7) were established by X-ray crystallography. The latter represents the first example of asymmetric coordination of selenolate ligands in binuclear bis chalcogenolate complexes of palladium and platinum. Thermolysis of [Pd(SeCb^oPh)₂(PEt₃)₂] (2) in HDA (hexadecylamine) at 330 °C gave nano-crystals of Pd₁₇Se₁₅.     

Triazole‐Functionalized N‐Heterocyclic Carbene Complexes of Palladium and Platinum and Efficient Aqueous Suzuki–Miyaura Coupling Reaction

Imidazolium salts bearing triazole groups are synthesized via a copper catalyzed click reaction, and the silver, palladium, and platinum complexes of their N‐heterocyclic carbenes are studied. [Ag₄(L1)₄](PF₆)₄, [Pd(L1)Cl](PF₆), [Pt(L1)Cl](PF₆) (L1=3‐((1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)methyl)‐1‐(pyrimidin‐2‐yl)‐1H‐imidazolylidene), [Pd₂(L2)₂Cl₂](PF₆)₂, and [Pd(L2)₂](PF₆)₂ (L2=1‐butyl‐3‐((1‐(pyridin‐2‐yl)‐1H‐1,2,3‐triazol‐4‐yl)methyl)imidazolylidene) have been synthesized and fully characterized by NMR, elemental analysis, and X‐ray crystallography. The silver complex [Ag₄(L1)₄](PF₆)₄ consists of a Ag₄ zigzag chain. The complexes [Pd(L1)Cl](PF₆) and [Pt(L1)Cl](PF₆), containing a nonsymmetrical NCN ′ pincer ligand, are square planar with a chloride trans to the carbene donor. [Pd₂(L2)₂Cl₂](PF₆)₂ consists of two palladium centers with CN₂Cl coordination mode, whereas the palladium in [Pd(L2)₂](PF₆)₂ is surrounded by two carbene and two triazole groups with two uncoordinated pyridines. The palladium compounds are highly active for Suzuki–Miyaura cross coupling reactions of aryl bromides and 1,1‐dibromo‐1‐alkenes in neat water under an air atmosphere.     

Synthesis and properties of Cu(II) and Pd(ii) complexes with chiral bis-α-sulfanyl oxymes,the derivatives of natural monoterpene, α-pinene

Coordination compounds Cu₂(H₂L¹)Cl₄ (I), Pd₂(H₂L¹)Cl₄ (II), Cu₂(H₂L²)Cl₄ (III), and Pd₂(H₂L²) Cl₄ (IV) with chiral bis-α-sulfanyloximes, the derivatives of the monoterpenoid (−)-α-pinene, were obtained. The complexes I and III are paramagnetic (μ_eff = 2.45 and 2.67 μ_B, respectively), II and IV are diamagnetic. According to IR spectroscopy, in the compounds I–IV the nearest environment of Cu and Pd atoms includes N, S, and Cl atoms. The values of μ_eff and parameters of ESR spectra of the solid phase and solutions of I and III show a binuclear structure of the Cu(II) complexes. Parameters of the ¹H and ¹³C NMR spectra of compounds II and IV indicate the formation of binuclear Pd(II) complexes of C ₂ symmetry and the closure of fivemembered chelate rings PdNSC₂. The PdCl₂ fragments are in transoid position. H₂L¹ and H₂L² are tetradentate bridging chelating ligands.     

Metal complexes of sulfur-nitrogen chelating agents. Part 12. The chemistry of nickel(II), palladium(II), cobalt(II) and copper(II) complexes of N2S2 and N3S2 donor systems

Summary Nickel(II), palladium(II), cobalt(II) and copper(II) complexes of the ligandN,N-1,2-propane-bis(methyl 2-amino-cyclopent-1-ene-dithiocarboxylate) (H₂L¹),N,N-1,3-propane-bis(methyl 2-aminocyclopent-1-ene-dithiocarboxylate) (H₂L²) andN,N-[bis(methyl 2-aminocyclopent-1-ene-dithiocarboxylate)] diethylenetriamine (H₂L³) have been synthesised. Both H₂L¹ and H₂L² form complexes of the type ML, and all but the copper(II) complexes, are square planar. In the copper(II) complexes tetrahedral distortion is significantly more with CuL². From H₂L³ square planar complexes of the type [M(HL³)X] (M=Ni, X=Cl, Br, I or SCN; M=Pd, X=Cl or Br) have been obtained in which the donor unit involved is N₂SX. The composition of the cobalt(II) and copper(II) complexes is [M(H₂L³)X₂] (X=Cl or Br) which contain the chromophore [MN₃X₂].     

Cyclooctenyl complexes of palladium(II) with multidentate N-heterocycles

[Pd(cod)(cotl)]ClO₄ (cod = 1,5-cyclooctadiene, cotl = cyclooctenyl, C₈H₁₃ ^–) undergoes substitutions with multidentate N-heterocycles: 1,3-bis(benzimidazolyl)benzene (L¹), 1,3-bis(1-methylbenzimidazol-2-yl)benzene (L²), 2,6-bis(benzimidazolyl)pyridine (L³) and 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (L⁴) to yield mono/binuclear complexes: [Pd(cotl)(L¹)(OClO₃)], [Pd(cotl)(L)]ClO₄ (L = L² or L³) and [Pd(cotl)₂(L⁴)](ClO₄)₂. Dihalobridged binuclear complexes [PdX(cotl)]₂ (X = Cl or Br) undergo halogen bridge cleavages with the multidentate N-heterocycles to form binuclear complexes of the type [PdX(cotl)₂L] (X = Cl or Br; L = L¹, L², L³ or L⁴). The complexes were characterized by elemental analyses, ¹H-, ¹³C-n.m.r., i.r., far-i.r. and FAB-mass spectral studies.     

Syntheses,characterization and anti‐microbial activities of palladium(II) and palladium(IV) complexes of 3,10‐C‐meso‐Me8[14]diene (L1) and its reduced isomeric anes (LA,LB and LC). Crystal and molecular structure of [PdL1][Pd(SCN)4]

The reactions of 3,10‐C‐meso‐3,5,7,7,10,12,14,14‐octamethyl‐1,4,8,11‐tetraazacyclotetradecadiene, L¹, and two isomers (L_B and L_C, differing in the orientation of methyl groups on the chiral carbon atoms) of its reduced form with PdCl₂ and K₂[Pd(SCN)₄], produce square‐planar tetrachloro‐ and tetrathiocyano‐palladium(II) complexes of general formulae [PdL′][PdCl₄] and [PdL′][Pd(SCN)₄] (L′ = L¹, L_B and L_C), respectively. By contrast, the third ane isomer, L_A, upon reaction with the same reagents, PdCl₂ and K₂[Pd(SCN)₄], formed octahedral tetrachloro‐ and tetrathiocyanato‐palladium(IV) complexes [PdL_ACl₂]Cl₂ and [PdL_A(SCN)₂](SCN)₂, respectively. The [PdL′][PdCl₄] and [PdL_ACl₂]Cl₂ complexes undergo substitution reactions with KSCN to form square‐planar and octahedral tetrathiocyanato complexes [PdL′][Pd(SCN)₄] and [PdL_A(SCN)₂](SCN)₂, respectively. All complexes have been characterized on the basis of analytical, spectroscopic, conductometric and magnetochemical data. The anti‐fungal and anti‐bacterial activities of these complexes have been studied against some phytopathogenic fungi and bacteria. The crystal structure of [PdL¹][Pd(SCN)₄] has been confirmed by X‐ray crystallography and shows with square‐planar PdN₄ and PdS₄ geometries [monoclinic, space group C2/c, a = 17.884(3) Å, b = 14.734(2) Å, c = 11.4313(18) Å, β = 104.054(5)° ]. Copyright © 2008 John Wiley & Sons, Ltd.