Antitumor and antimycobacterial activities of cyclopalladated complexes: X-ray structure of [Pd(C-2,N-dmba)(Br)(tu)] (dmba = N,N-dimethylbenzylamine, tu = thiourea)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Synthesis and characterization of mono and polymeric cyclopalladated compounds: Crystal and molecular structure of [{Pd(dmba)(ONO2)}(2)(mu-pz)] center dot H2O (pz = pyrazine)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Self-assembly of cyclometallated Pd(II) compounds directed by C-H center dot center dot center dot pi interactions: A structural evidence for metalloaromaticity in a cyclopalladated ring

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Binuclear cyclopalladated compounds with antitubercular activity: synthesis and characterization of [{Pd(C-2,N-dmba)(X)}(2)(mu-bpp)] (X = Cl, Br, NCO, N-3; bpp=1,3-bis(4-pyridyl)propane)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermal and spectroscopic investigation on N,N-dimethylbenzylamine based cyclopalladated compounds containing isonicotinamide

Synthesis, spectroscopic characterization and thermal analysis of the [Pd(dmba)(Cl)(iso)] (1), [Pd(dmba)(NCO)(iso)] (2), [Pd(dmba)(N(3))(iso)] (3) and [Pd(dmba)(Br)(iso)] (4) (dmba = N,N'-dimethylbenzylamine; iso = isonicotinamide) compounds are described in this work. The complexes were investigated by infrared spectroscopy (IR), differential thermal analysis (DTA) and thermogravimetry (TG) and the residues of the thermal decomposition were identified as Pd(o) by X-ray powder diffraction. The thermal stability order of the complexes varied as [Pd(dmba)(Cl)(iso)] (1) > [Pd(dmba)(Br)(iso)] (4) > [Pd(dmba)(NCO)(iso)] (2) > [Pd(dmba)(N(3))(iso)] (3).

1,3-dipolar cycloaddition of CS2 to the coordinated azide in the cyclopalladated [Pd(bzan)(mu-N-3)](2). Crystal and molecular structure of di(mu-N,S-1,2,3,4-thiatriazole-5-thiolate)bis[(benzylideneaniline-C-2,N)palladium(II)]

The compound [Pd(bzan)(mu -N-3)](2) 1, bzan = benzylideneaniline, was prepared from [Pd(bzan) (mu -OOCCH3)](2) by an anion exchange reaction. The 1,3-dipolar cycloaddition of carbon disulfide to the bridged coordinated azide in the cyclometallated compound I was investigated. The species resulting from this reaction, di(mu -N,S-1,2,3,4-thiatriazol-5-thiolate)bis[(benzylideneaniline)palladium(II)] 2, was characterized by IR spectroscopy and X-ray diffraction. The compound 2 is a dimer containing two [Pd(benzylideneaniline)] moieties connected by two vicinal bridging N,S-1,2,3,4-thiatriazole-5-thiolate anions in a square-planar coordination geometry for the palladium atoms.

Self-assembly of organometallic Pd(II) complexes via CH3 center dot center dot center dot pi interactions: the first example of a cyclopalladated compound with herringbone stacking pattern

Two binuclear cyclometallated compounds [Pd(C-2,N-dmba)(mu-N-3)](2) (1) and [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] (2) (dmba = N,N-dimethylbenzylarnine) have been synthesized and characterized by elemental 3 analysis, IR and NMR spectroscopies and single crystal X-ray diffraction crystallography. The ability of CH3 groups to form C(sp(3))-H...pi hydrogen bonds with phenyl rings is responsible for the molecular self-assembly within the crystals of 1 and 2. Compound 1 crystallizes as one-dimensional supramolecular chains whereas the crystal packing of 2 consists of a herringbone of sandwiches composed by two inversely related [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] molecules. (c) 2007 Elsevier B.V. All rights reserved.

Thermal study of cyclopalladated complexes of the type [Pd-2(dmba)(2)X-2(bpe)] - (X=NO3-, Cl-, N-3(-), NCO-, NCS-; bpe=trans-1,2-bis(4-pyridyl)ethylene)

The synthesis, characterization and thermal analysis of the novel cyclometallated compounds [Pd-2(dmba)(2)Cl-2(mu-bpe)] (1), [Pd-2(dmba)(2)(N-3)(2)(mu-bpe)] (2), [Pd-2(dmba)(2)(NCO)(2)(mu-bpe)] (3), [Pd-2(dmba)(2)(SCN)(2)(mu-bpe)] (4), [Pd-2(dmba)(2)(NO3)(2)(mu-bpe)] (5) (bpe=trans-1,2-bis(4-pyridyl)ethylene; dmba=N,N-dimethylbenzylamine) are described. The thermal stability of [Pd-2(dmba)(2)X-2(mu-bpe)] complexes varies in the sequence 1 > 4 > 3 > 2 > 5. The final residues of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction.

Thermal and spectroscopy investigation of cyclopalladated compounds of the type [Pd(C(1)3H(1)0N)(mu-X)](2), (X=H3CCOO, NCO, SCN, CN)

The dimeric compound [Pd(bzan)(mu-OOCCH3)](2) (1) (bzan=N-benzylideneaniline) reacts with KX, in methanol/acetone (2:1), affording the analogous dimeric pseudohalogen-bridged species [Pd(bzan)(mu-X)](2) [X=NCO(2), SCN(3), CN(4)]. The compounds were characterized by elemental analysis, infrared spectroscopy, NMR and thermogravimetric analysis. IR data for 2-4 showed bands typical of coordinated pseudohalogen ligands clearly indicating the occurrence of the exchange reaction. Their thermal behaviour was investigated and suggested that their stability is influenced by the bridging ligand. The thermal stability decreased in the order [Pd(bzan)(mu-CN)](2)>[Pd(bzan)(mu-SCN)](2)>[Pd(bzan)(mu-OOCCH3)](2)>[Pd(bzan)(mu-NCO)](2). X-ray results showed the formation of Pddegrees as final decomposition product.

Cleavage of the dimeric cyclopalladated [Pd(N,C-dmba)(mu-X)](2), (dmba = N,N-dimethylbenzylamine; X = SCN and NCO) by diphosphines. Palladium(II) compounds with distinct structures in the solid-state and in solution

The reactions of the pseudohalide-bridged dimer [Pd(N,C-dmba)(mu -SCN)](2) (1) (dmba = N,N-dimethylbenzylamine) with cis-Ph2PCH=CHPPh2 (cis-dppet) (1:1 molar ratio) and of [Pd(N,C-dmba)(mu -NCO)](2) (2) with Ph2PCH2CH2PPh2 (dppe) (1:2 molar ratio) gave mononuclear [Pd(C-dmba)(SCN)(cis-dppet)].H2O (1a) and [Pd(C-dmba)(NCO)(dppe)] (2a), respectively, with the diphosphines acting as chelating ligands. Reaction of (2) with Fe(C5H4PPh2)(2) (dppf) (1:1 molar ratio) yielded [{Pd(N,C-dmba)(NCO)}(2)(mu -dppf)] (2b), a bimetallic species containing two palladium atoms bridged by the diphosphine, whereas reaction in a 1:2 molar ratio gave the mononuclear [Pd(N,C-dmba)(dppf)][NCO]. CH2Cl2 (2c), with the diphosphine acting as a chelating ligand. The compounds have been characterized by elemental analysis, i.r., P-31{H-1}, C-13- and H-1-n.m.r. spectroscopies. Conductivity measurements together with spectroscopic data showed that (1a) and (2a) do not have the same structure in the solid state and in MeCl solution, whereas for compounds (2b) and (2c) no structural changes were observed when the solids were dissolved in MeCl.

SYNTHESIS AND CRYSTAL-STRUCTURE OF THE NOVEL CYCLOPALLADATED COMPLEX DI(MU,N-S-ETA(2)-QUINOLINE-2-THIOLATE)-BIS[(N,N-DIMETHYLBENZYLAMINE-C(2),N) PALLADIUM(II)]

The compound di(mu,N-Seta2-2-quinoline-2-thiolate)-bis[(N,N-dimethylbenzylamine-C2,N)palladium(II)] was synthesized and studied by IR, NMR and X-ray diffraction: monoclinic, a = 20.138(3), b = 10.831(1), c = 14.973(2) angstrom, beta = 98.04(1)-degrees, Z = 4, space group P2(1)/c, R = 0.032. The compound is dimeric with the two [Pd(N,N-dimethylbenzylamine)]moieties being connected by the two vicinal bridging eta2-N,S-quinoline-2-thiolate anions in a square-planar coordination geometry for the palladium atoms.

Thermal Behavior and Spectroscopic Study of Neutral and Cationic Mononuclear Cyclopalladated Compounds

The reactions of the precursor [Pd(N,C-dmba)(MeCN)2](NO 3) (1) (dmba = N,N-dimethylbenzylamine), with the proligands 3,5-dimethylpyrazole (Hdmpz), 2-quinolinethiol (qnSH) and 1,1′- bis(diphenylphosphine)ferrocene (dppf) afforded the compounds [Pd(N,C-dmba)(Hdmpz)(ONO2)]0.5CH2Cl2 (2), [Pd(N,C-dmba)(qnSH)(ONO2)] 0.5CH2Cl2 (3) and [Pd(N,C-dmba)(dppf)](NO3) (4), respectively. The mononuclear species 2,3 and 4 were characterized by elemental analysis, infrared spectroscopy, NMR and thermogravimetric analysis. The IR spectra show bands which are consistent with terminal monodentate nitrate group for 2-3 and ionic nitrate for 4. The 1H and 13C NMR data confirm that coordination of the organic ligands has occurred and the 31P{1H} NMR data for 4 clearly evidences the occurrence in solution of three cyclopalladated species with the dppf acting as a bridging ligand in two cases and as a chelate in one. The thermal behavior of compounds 1-4 suggests that complex 2 is the most stable. The X-ray diffractometry results show the formation of PdO from 1 and 2, Pd2OSO4 from 3, and of a mixture of PdO and Fe 2(PO4)3 from 4, as final decomposition products.

Asymmetric and Symmetric Triazenido Cyclopalladated Complexes: Synthesis, Structural Analysis and DFT Calculations

The reaction of [Pd{dmba}(l-N3)]2 (dmba = N,N-dimethylbenzylamine) with 1-(2-fluorophenyl)-3-(4- nitrophenyl)triazenido (L1 ) or 1,3-bis(4-nitrophenyl)triazenido (L2 ) anions, in methanol, and subsequent treatment with pyridine (py) allows the preparation of the corresponding cyclopalladated compounds [Pd(dmba)(L1 )(py)] (1) and [Pd(dmba)(L2 )(py)]py (2). The acentric mononuclear entities of (1) and (2) are connected by weak intermolecular non-classical CAHC hydrogen bonds, which results in 2-D arrangements by translation, along the [1 0 0] and [0 01] crystallographic directions, respectively.

C-2, N-dimethylbenzylamine cyclopalladated compounds: evaluation of cytotoxic, mutagenic and antitubercular activities

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis, characterization and thermal behavior of cyclopalladated compounds of the type [Pd{C6H4CH2N(CH3)(2)}(mu-X)](2) (X= Cl, NCO, SCN, CN)

The dimeric compound [Pd(dmba)(μ-Cl)]2 (1) (dmba = N,N-dimethylbenzylamine) reacts with KX, in methanol/acetone, affording the analogous dimeric pseudohalide-bridged species [Pd(dmba)(X)]2 [X = NCO(2), SCN(3), CN(4)]. The compounds were characterized by elemental analysis, infrared spectroscopy, NMR and thermogravimetric analysis. The IR data for 2-4 showed bands typical of coordinated pseudohalide ligands indicating clearly the occurrence of the exchange reaction. Their thermal behavior was investigated and suggested that their thermal stability is influenced by the bridging ligand. The thermal stability decreased in the order [Pd(dmba)(μ-SCN)]2>[Pd(dmba)(μ-Cl)] 2>[Pd(dmba)(;u-NCO)]2>[Pd(dmba)(μ-CN)]2. The X-ray results showed the formation of PdO as final decomposition product. © 1999 Elsevier Science Ltd. All rights reserved.