Interaction of adenine with dichloro-[1-alkyl-2-(naphthylazo)-imidazole]palladium(II) complexes: kinetic and mechanistic studies

Interaction of adenine (A) with dichloro-[1-alkyl-2-(α-naphthylazo)imidazole] palladium(II) [Pd(α-NaiR)Cl₂], 1 and dichloro-[1-alkyl-2-(β-naphthylazo)imidazole] palladium(II) [Pd(β-NaiR)Cl₂], 2 {where R=Me (a), Et (b) or Bz (c)} in MeCN-water (50% v/v) medium to yield [{1-alkyl-2-(α-naphthylazo)imidazole}(adenine)]palladium(II) perchlorates (3a, 3b, 3c) and [{1-alkyl-2-(β-naphthylazo)imidazole}(adenine)]palladium(II) perchlorates (4a, 4b, 4c) was studied. The products were characterized by physico-chemical and spectroscopic methods. The reaction kinetics were second order overall, being first order in both the Pd(II) complex and adenine. The effect of adding chloride was consistent with rate-limiting dissociation of chloride from the complex. Thermodynamic parameters were determined from temperature variation experiments. The second-order rate constant k ₂ corroborates with the experimental Δ^‡H° values, while the negative values of Δ^‡S° indicate that the reaction proceeds through an associative inner sphere mechanism.     

Pd–Cl cleavage of dichloro-[1-alkyl-2-(naphthylazo)imidazole]palladium(II) complexes by picolinic acid: Kinetic and mechanistic studies

Picolinic acid (picH) reacts with [Pd(α-/β-NaiR)Cl₂] [α-/β-NaiR = 1-alkyl-2-(naphthyl-α-/β-azo)imidazole] in acetonitrile (MeCN) medium to give [Pd(α-/β-NaiR)(pic)](ClO₄). The products are characterized by spectroscopic techniques (FT-IR, UV–Vis, NMR). The reaction kinetics show first order dependence of rate on each of the concentration of Pd(II) complex and picH. Addition of LiCl to the reaction decreases the rate of reaction and has proved the cleavage of Pd–Cl bond at the rate-determining step. Thermodynamic parameters (Δ^‡H° and Δ^‡S°) are determined from variable temperature kinetic studies. The magnitude of the second order rate constant, k₂ increases as in the order: Pd(NaiEt)Cl₂ < Pd(NaiMe)Cl₂ <  Pd(NaiBz)Cl₂ as well as Pd(β-NaiR)Cl₂ <  Pd(α-NaiR)Cl₂.     

Synthesis and characterization of palladium(II) complexes of thioureas. X-ray structures of [Pd( N , N ′-dimethylthiourea)4]Cl2?·?2H2O and [Pd(tetramethylthiourea)4]Cl2

Palladium(II) complexes of thiones having the general formula [Pd(L)₄]Cl₂, where L = thiourea (Tu), methylthiourea (Metu), N,N′-dimethylthiourea (Dmtu), and tetramethylthiourea (Tmtu) were prepared by reacting K₂[PdCl₄] with the corresponding thiones. The complexes have been characterized by elemental analysis, IR and NMR spectroscopy, and two of these, [Pd(Dmtu)₄]Cl₂ · 2H₂O (1) and [Pd(Tmtu)₄]Cl₂ (2), by X-ray crystallography. An upfield shift in the >C=S resonance of thiones in ¹³C NMR and downfield shift in N–H resonance in ¹H NMR are consistent in showing sulfur coordination with palladium(II). The crystal structures of the complexes show a square-planar coordination environment around the Pd(II) ions with the average cis and trans S–Pd–S bond angles of 89.64° and 173.48°, respectively. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. An erratum to this article can be found at     

Platinum group metal functionalized phosphine complexes. Part 2. Phosphinoamide rhodium(I), iridium(I), palladium(II) and platinum(II) complexes

Summary Rhodium(I), iridium(I), palladium(II) and platinum(II) complexes of the phosphinoamide ligands, Ph₂PCH₂CONHR (R = H, HDPA; Me, MDPA; Ph, PDPA) were prepared and characterized by using conductivity data, i.r., ¹H and ³¹P(H) n.m.r. spectral data. Reaction of the ligands with MCl(PPh₃)₃ and MCl(CO)(PPh₃)₂ (M = Rh, Ir) in CH₂Cl₂ under reflux lead to the formation of MCl(PPh₃)₂ [Ph₂PCH₂C(O)NHR] and MCl(CO)(PPh₃)[Ph₂PCH₂–C(O)HNR] respectively. The reaction of either K₂MCl₄ or cis-MCl₂(PPh₃)₂ affords complexes of the type cis-MCl₂[Ph₂PCH₂C(O)NHR]₂ (M = Pd, Pt). A similar product results even from the reaction of phosphinoamides with cis-platin. Possible structures are proposed for the complexes based on their physicochemical data     

Mechanistic studies on the Pd–Cl cleavage of dichloro-[1-alkyl-2-(naphthylazo)imidazole]palladium(II) complexes by 8-quinolinol

8-Quinolinol (HQ) reacts with [Pd(α-/β-NaiR)Cl₂] [α-/β-NaiR = 1-alkyl-2-(naphthyl-α-/β-azo)imidazole] in acetonitrile (MeCN) solution to give [Pd(α-/β-NaiR)(Q)](ClO₄). The products are characterized by spectroscopic techniques (FT-IR, UV–Vis, NMR). The reaction kinetics show a first order dependence of rate on each of the concentration of the metal complex and HQ. Addition of LiCl to the reaction retarded the rate of reaction and has proved the cleavage of the Pd–Cl bond as the rate-determining step. Thermodynamic parameters (Δ^‡H^° and Δ^‡S^°) are determined from variable temperature kinetic studies. The magnitude of the second order rate constant, k₂, increases as in the order: Pd(NaiEt)Cl₂ < Pd(NaiMe)Cl₂ < Pd(NaiBz)Cl₂ as well as Pd(β-NaiR)Cl₂ < Pd(α-NaiR)Cl₂.     

Palladium(II) complexes with 1-allyl-3-(2-pyridyl)thiourea: Synthesis and spectroscopic characterization

New Pd(II) complexes with 1-allyl-3-(2-pyridyl)thiourea (APTU) of the formulas [Pd(C₉H₁₁N₃S)Cl₂] (I) and [Pd(C₉H₁₁N₃S)₂]Cl₂ (II) were obtained and examined by UV-Vis, IR, and 1H NMR spectroscopy. The conditions for the complexation reactions were optimized. The instability constants and molar absorption coefficients of these complexes were calculated. Comparison of the characteristic bands in the UV-Vis and IR spectra of the complexes and free APTU revealed that the ligand in both complexes is coordinated to the metal atom in the thione form in the bidentate chelating mode through the S atom of the thiourea group and the pyridine N atom. In the UV-Vis spectra of the complexes, the charge transfer bands (π → π* Py) and n → π* (C=N_Py), (C=S) experience hypsochromic shifts by 450–470 cm⁻¹ caused by the coordination of APTU to the metal ion, which gives rise to ligand-metal charge-transfer bands (C=N_Py → Pd, n → π* (C=S)) and (SPd). The protons in the 6-, 4-, and 3-positions of the pyridine ring and the thiourea NH proton in the chelate ring are most sensitive to the complexation.     

Palladium(II) and Platinum(II) Complexes with Bisphosphanes, [S2C=C(CN)2]2– and [Se2C=C(CN)2]2– as Chelating Ligands

The palladium(II) and platin(II) 1, 1‐dicyanoethylene‐2, 2‐dithiolates [(L–L)M{S₂C=C(CN)₂}] (M = Pd: L–L = dppm, dppe, dcpe, dpmb; M = Pt: dppe, dcpe, dpmb) were prepared either from[(L–L)MCl₂] and K₂[S₂C=C(CN)₂] or from [(PPh₃)₂M{S₂C=C(CN)₂}] and the bisphosphane. Moreover, [(dppe)Pt{S₂C=C(CN)₂}]was obtained from [(1, 5‐C₈H₁₂)Pt{S₂C=C(CN)₂}] and dppeby ligand exchange. The 1, 1‐dicyanoethylene‐2, 2‐diselenolates[(dppe)M{Se₂C=C(CN)₂}] (M = Pd, Pt) were prepared from[(dppe)MCl₂] and K₂[Se₂C=C(CN)₂]. The oxidation potentials of the square‐planar palladium and platinum complexes were determined by cyclic voltammetry. The reaction of [(dcpe)Pd(S₂C=O)] with TCNE led to a ligand fragment exchange and gave the 1, 1‐dicyanoethylene‐2, 2‐dithiolate [(dcpe)Pd{S₂C=C(CN)₂}] in good yield.     

Synthesis,spectral and electrochemical characterization of (dithiocarbamato)(arylazoimidazole)Palladium(II) perchlorates

The ternary complexes [Pd(RaaiX)(SS)ClO₄) where RaaiX is a N(1)-alkyl-2-(arylazo)imidazole (p-RC₆H₄N =NC₃H₂NN(1) X; X = Me, or Et, and R = H, Me or Cl) and SS = N,N-diethyldithiocarbamate or morpholinedithiocarbamate have been prepared and characterized by elemental analysis, i.r., u.v.-vis. and ¹H-n.m.r. data. Electrochemical studies show azo reduction. The complexes are thermally unstable and decompose to bis(dithiocarbamato)palladium(II) in solution. This revised version was published online in June 2006 with corrections to the Cover Date.     

Palladium(II) N-heterocyclic carbene complexes: synthesis,structures and cytotoxicity potential studies against breast cancer cell line

Abstract

Mononuclear trans-Pd(II)–NHC complexes (where NHC?=?N-heterocyclic carbene) bearing asymmetrically substituted NHC-ligand have been synthesized via transmetalation reaction between Ag(I)–NHC complexes and [Pd(NCCH₃)₂Cl₂]. The NHC precursors are accessible in two steps by N-n-alkyl reactions of benzimidazole. The resultant benzimidazolium salts were deprotonated with Ag₂O by in situ deprotonation to facilitate the formation of mononuclear Ag(I)–NHC complexes. Single-crystal structural study for Pd(II)–NHC shows that the palladium(II) ion exhibits a square-planar geometry of two NHC ligands and two chloride ions. The cytotoxicity study was investigated against breast cancer cell line (MCF-7). The Ag(I)–NHC complexes exhibit better activities than their corresponding Pd(II)–NHC complexes, whereas all benzimidazolium salts are inactive toward MCF-7 cancer cell line.     

Thermal Decomposition of Cu(II) Complexes with 2-Chloro- and 2,6-Dichlorobenzoic Acid and Imidazole

The reaction products of Cu(II) 2-chlorobenzoate and the imidazole (1), and of Cu(II) 2,6-dichlorobenzoate and the imidazole (2) formulated as CuL’₂⋅2imd⋅2H₂O and CuL”₂⋅2imd⋅2H₂O (L’=C₇H₄ClO₂ ⁻, L”=C₇H₃Cl₂O₂ ⁻, imd=imidazole), were prepared and characterized by means of spectroscopic measurements and thermochemical properties. The blue (1) and green (2) complexes were obtained as solids with a 1:2:2 molar ratio of metal to carboxylate ligand to imidazole. When heated at a heating rate of 10 K min⁻¹ the hydrated complexes, (1) and (2), lose some of the crystallization water molecules and then decompose to gaseous products. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ethylenediamine and 1,10-phenanthroline biscyclometallated complexes of Pd(II) and Pt(II) based on 4,6-diphenylpyrimidine

Biscyclometallated [(M(N∧N))₂(μ-dphpm)](ClO₄)₂ and [(N∧N)Pd(μ-dphpm)Pt(N∧N)]Cl₂ complexes [M = Pd(II), Pt(II); (N∧N) ethylenediamine (En), 1,10-phenanthroline (phen); dphpm² — bisdeprotonated form of 4,6-diphenylpyrimidine)] have been characterized by the ¹H NMR, electronic absorption and emission spectroscopy, and also cyclic voltammetry methods. The lowest unoccupied molecular orbital (LUMO) of biscyclometallated complexes with ethylenediamine, responsible for low-energy photo- and electro-stimulated processes irrespective of the metal nature, is assigned to the π* orbital mainly localized on the pyrimidine part of the bridging ligand. In the case of complexes with phenanthroline chelating ligands, the replacement of one or two palladium metal centers [{Pd(phen)}₂(μ-dphpm)]²⁺ by platinum centers changes the LUMO nature of the complexes for the π* orbital mainly localized on the peripheral metal-complex fragment {Pt(phen)}.     

Reduction of palladium(II) monoglycinate complexes at rotating disc palladium electrode in acid media

Reduction of palladium(II) glycinate complexes in strongly acid 0.5 M NaClO₄ solutions (pH 0.6 and 1.0) with variable palladium(II) complex and free glycine concentration was studied by the taking of cyclic voltammograms at palladium rotating disc electrode. It is shown that it was a chelate monoglycinate palladium(II) complex that was present in all studied solutions and underwent the reduction. The diffusion coefficient of the chelate monoglycinate palladium(II) complex D = (6.5 ± 0.5) × 10⁻⁶ cm²/s was determined from the limiting diffusion current of the complex reduction. The monoglycinate palladium(II) complex reduction occurred in the double-layer segment of the palladium charging curve; it was not complicated by hydrogen adsorption at electrodes. The palladium(II) complex reduction half-wave potential was determined (E _1/2 = ∼0.300 to 0.330 V (SCE)). It is shown that the decreasing of the number of ligands coordinated by palladium via nitrogen atom facilitates the complex reduction process. In particular, the reduction potentials of palladium(II) complexes with different ligand number at palladium electrode shifted markedly toward negative potentials in the series: Pdgly⁺ < Pd(gly)2 < Pd(gly)₄²⁻.     

A study of the reactions of methionine- and histidine-containing peptides with palladium(II) complexes: The key role of steric crowding on palladium(II) in the selective cleavage of the peptide bond

¹H NMR spectroscopy was applied to study the reactions of palladium(II) complexes, cis-[Pd(dpa)Cl₂] and cis-[Pd(dpa)(H₂O)₂]²⁺ (dpa is 2,2′-dipyridylamine acting as a bidentate ligand) with the dipeptides methionylglycine (Met-Gly) and histidylglycine (His-Gly), and the N-acetylated derivatives of these dipeptides, MeCOMet-Gly and MeCOHis-Gly. All reactions were carried out in the pH range 2.0–2.5 with equimolar amounts of the palladium(II) complex and the peptide at two different temperatures, 25 and 60 °C. In the reactions of cis-[Pd(dpa)Cl₂] and cis-[Pd(dpa)(H₂O)₂]²⁺ with Met-Gly and His-Gly, no hydrolysis of the peptide bond was observed. The final product in these reactions was the [Pd(dpa)₂]²⁺ complex. The square-planar structure of this complex was confirmed by X-ray analysis. The reaction of the cis-[Pd(dpa)(H₂O)₂]²⁺ complex with the MeCOHis-Gly and MeCOMet-Gly peptides under the previously mentioned experimental conditions was remarkably selective in the cleavage of the amide bond involving the carboxylic group of methionine in the side chain. The modes of coordination of cis-[Pd(dpa)Cl₂] and cis-[Pd(dpa)(H₂O)₂]²⁺ in the reactions with the non-acetylated peptides and the total steric inhibition of the hydrolytic reaction between cis-[Pd(dpa)(H₂O)₂]²⁺ and MeCOHis-Gly can be attributed to the steric bulk of the palladium(II) complex. This finding should be taken into consideration in designing new palladium(II) complexes for the regioselective cleavage of peptides and proteins.     

Quantum chemical modeling of nucleophilic substitution reactions in the complexes cis-Pt(NH3)2Cl2 and cis-Pd(NH3)2Cl2

The B3LYP/6-31G** method was used for the study of nucleophilic substitution reaction in platinum and palladium square-planar cis-diaminate complexes. The processes under consideration take place in two steps through pentacoordinated transition states. Activation barriers for both steps of these processes in gaseous phase and aqueous solution were calculated. A major role in the increase in the activation energies is played by the formation of the intermediate electrostatic Van der Waals’ complexes. For the complex cis-[Pd(NH₃)₂Cl₂], the activation barriers in the nucleophilic substitution reaction are considerably lower than those for the complex cis-[Pt(NH₃)₂Cl₂].     

Benign synthesis of quinolinecarboxamide ligands,H2bqbenzo and H2bqb and their Pd(II) complexes: X-ray crystal structure,electrochemical and antibacterial studies

Two carboxamide ligands, H₂bqbenzo {3,4-bis(2-quinolinecarboxamido)benzophenone} and H₂bqb {N,N′-bis[(2-quinolinecarboxamide)-1,2-benzene]}, have been prepared using tetrabutylammonium bromide as an environmentally benign reaction medium. Two new Pd(II) complexes, [Pd^II(bqbenzo)] (1) and [Pd^II(bqb)] (2), have been synthesized, characterized, and their structures determined by single crystal X-ray diffraction. The di-anionic ligands, bqbenzo^2? and bqb^2?, are coordinated via two N_amide atoms and the nitrogens of the two quinoline rings, with Pd?N_amide < Pd–N_quinoline bond lengths. The geometry around palladium(II) in both complexes is distorted square planar. The electrochemical behaviors of the ligands and their Pd(II) complexes have been investigated by cyclic voltammetry in DMF. An irreversible Pd^II/I reduction is observed at ?1.06 V for 1 and at ?1.177 V for 2, indicating the influence of the R substituent on the central phenyl ring of carboxamide ligands on the Pd^II/I reduction potential. The ligands and palladium complexes were also screened for in vitro antibacterial activity. The Pd(II) complexes show strong biological activity against S.typhi and E.coli as Gram ?ve and B.cereus and S.aureus as Gram +ve bacteria comparable to the antibiotic penicillin. The antibacterial results also reveal that coordination of Pd(II) significantly improves the activity.     

Synthesis, characterization and cytotoxicity of some palladium(II), platinum(II), rhodium(I) and iridium(I) complexes of ferrocenylpyridine and related ligands. Crystal and molecular structure of trans-dichlorobis(3-ferrocenylpyridine)palladium(II)

The preparation of a series of ferrocenyl nitrogen donor ligands including ferrocenylpyridines, ferrocenylphenylpyridines and 1,1^′-di(2-pyridyl)ferrocene is described. Coordination studies of the substituted pyridines (L) were carried out with platinum, palladium, rhodium and iridium. This resulted in the preparation of the following types of complexes: [MCl(CO)₂(L)] and [M(cod)(L)₂]ClO₄ where M=Rh or Ir, cod=1,5-cyclooctadiene; [M^′Cl₂(L)₂] where M^′=Pt or Pd. The X-ray crystal structure of trans-dichlorobis(3-ferrocenylpyridine)palladium was obtained. The complexes were screened for activity against two human cancer cell lines. At least two of the complexes displayed growth inhibition similar to that of the widely used chemotherapeutic agent, cisplatin.     

Palladium(II) complexes with 5-methyl-5-(4-pyridyl)-2,4-imidazolidenedione

Two new palladium(II) complexes with 5-methyl-5-(4-pyridyl)-2,4-imidazolidenedione(mpyh) were synthesized: cis-[Pd(mpyh)₂Cl₂]·H₂O and cis-[Pd(mpyh)₂Br₂]·2H₂O. The molecular formulae of the complexes were confirmed by elemental analysis, IR, ¹H NMR spectra and DTA study. The ligand is coordinated to the palladium ion with N-atom of the pyridine ring. The spectroscopic data indicate a square planar geometry with two N-pyridine atoms and two halogene anions in cis position. The final product of the thermal decomposition of cis-[Pd(mpyh)₂Cl₂]·H₂O is metallic Pd, whereas for cis-[Pd(mpyh)₂Br₂]·2H₂O the residue consists of metallic Pd and C. The cytotoxic effects of the complexes were examined in vitro on some human tumor cell lines. The cis-[Pd(mpyh)₂Cl₂]·H₂O proved to be more active as compared to the cis-[Pd(mpyh)₂Br₂]·2H₂O.     

Cis-coordination of the chromate anions in helical Co/Ni block-type polymeric systems. Structural and spectroscopic characteristics of catena(μ-CrO4-O,O′)[Co(HIm)3H2O] and catena(μ-CrO4-O,O′)[Co0.43Ni0.57(HIm)3H2O]

Two polymeric complexes: catena(μ-CrO₄-O,O′)[Co(HIm)₃H₂O] (1) and catena(μ-CrO₄-O,O′)[Co_0.43Ni_0.57(HIm)₃H₂O] (2) (where HIm=imidazole) with a cis-bridging coordination mode of the CrO₄ ²⁻ anion have been synthesized and characterized by X-ray and spectroscopic methods. These crystals were isolated from nine systems of varying reagent molar ratios and three excluding anions: Cl⁻, NO₃ ⁻ and SO₄ ²⁻ exclusively as mer [M(HIm)₃O₃]-type isomers. The unit cell of these isostructural complexes (monoclinic crystal system P2₁ /n) contains two independent helixes, left- and right handed, stabilized by intrahelical and interhelical hydrogen bonding and π–π interaction between pairs of the imidazole rings from neighbouring helixes. The Raman spectra at 77 K of 1 and 2 deconvoluted into lorentzian components revealed the block-type polymeric structure of the complexes. Moreover, the solution studies at millimolar concentrations of 1 and 2 indicated their complete decomposition in water. Four K electronic spectral analysis of the crystals (band deconvolution into gaussian components) enhanced with the data obtained in the polarized light allowed for assignment of the bands to the respective d–d transition (D_4h symmetry). It was found that the metallic centres are independently absorbing species, which supports the suggestion of a block-type structure of the polymers. The respective crystal field parameters for Co and Ni were calculated.     

Heterobimetallic complexes of cis-1,2-bis(diphenylphosphine)ethene containing tin and nickel,palladium or platinum

Summary New heterobimetallic complexes of nickel, palladium or platinum and the ligand cis-1,2-bis(diphenylphosphine)-ethene, dppen, and tin were prepared. The transition metal is bonded either directly or via chlorine bridges to the tin atom. The compounds were obtained from precursor complexes of the general formula [M(dppen)Cl₂] (M = Ni, Pd or Pt) by reaction with Ph₃SnH or SnCl₂.     

Synthesis, characterization and antimicrobial activity of palladium(II) complexes with some alkyl derivates of thiosalicylic acids: Crystal structure of the bis(S-benzyl-thiosalicylate)-palladium(II) complex, [Pd(S-bz-thiosal)2]

S-Alkyl (R = benzyl, methyl, ethyl, propyl and butyl) derivatives of thiosalicylic acid and the corresponding palladium(II) complexes were prepared and their structures were proposed on the basis of infrared, ¹H and ¹³C NMR spectroscopy. The cis geometrical configurations of the isolated complexes were proposed on the basis of an X-ray structural study of the bis(S-benzyl-thiosalicylate)-palladium(II), [Pd(S-bz-thiosal)₂] complex.Antimicrobial activity of the tested compounds was evaluated by determining the minimum inhibitory concentration (MIC) and minimum microbicidal concentration (MMC) in relation to 26 species of microorganisms. The tested ligands, with a few exceptions, show low antimicrobial activity. The palladium(II) complexes, [Pd(S-R-thiosal)₂], have statistically significant higher activity than the corresponding ligands. The complexes [Pd(S-et-thiosal)₂] and [Pd(S-pro-thiosal)₂] displayed the strongest activity amongst the all tested compounds. The palladium(II) complexes show selective and moderate antibacterial activity and significant antifungal activity. The most sensitive were Aspergillus fumigatus and Aspergillus flavus.