Synthesis, characterization and molecular structure of Pd(II) complex containing the methyl-hemiacetal form of isonicotinaldehyde (original) (raw)
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The reaction of PdCl 2 with 1-ethyl-3-phenyl-thiourea (Heptu), 3-mercapto-4-methyl-4H-1,2,4-triazole (Hmmtrz) and 2-mercapto-5-methyl-1,3,4-thiadiazole (Hmthd) respectively, yielded three new complexes [Pd(eptu) 2 ] (1), [Pd(Hmmtrz) 4 ]Cl 2 (2) and [Pd(Hmthd) 4 ]Cl 2 Á2CHCl 3 (3). These complexes have been isolated in pure form and characterized by elemental analyses, IR, NMR and single crystal X-ray diffraction technique. In all compounds the metal ion adopts a square-planar geometry. Two nitrogen and two sulfur atoms from the monoanionic eptu ligand in complex 1 are bonded to Pd(II) centre in trans fashion. Complexes 2 and 3 are salt-like and the metal centre is bonded through four neutral ligands. The electrical neutrality in these complexes is maintained by the presence of two chlorides as counter ions. Migration of hydrogen, within the ligand framework in complexes 2 and 3, from sulfur to nitrogen is observed that resulted in the thione form of the ligand and its coordination to the metal centre in both the complexes. Complex 2 is stabilized by intermolecular CAHÁ Á ÁN and intramolecular NAHÁ Á ÁCl hydrogen bonding leading to an extended structure. Complex 3 is stabilized by intermolecular CAHÁ Á ÁS hydrogen bonding. Complexes 1-3 are fluorescent materials which upon excitation at 31 000, 38 600 and 32 300 cm À1 exhibit an emission at 25 200, 27 000 and 26 700 cm À1 , respectively.
2017
Three cis-chelating diN -heterocyclic carbene palladium(II) complexes [Pd(X) 2 (di-NHC)] (X= tsac, sac and bit) tsac= thiosaccharinate, sac= saccharinate, bit= benzisothiazolinate, bearing different anionic co-ligand was synthesized and characterized. A series of palladium(II) complexes (2-5) bearing cis-chelating homo-dicarbene ligand with varying propylene-bridged (C3) and N-heterocyclic backbones (imidazole) have been synthesized by reaction of [Pd(OAc) 2 ] with the respective diazolium bromides in DMSO, have been prepared and characterized by elemental analysis, infrared spectra and 1 H NMR. These compounds are all stabilized in the sold state. The bidentate (diNHC) ligand together with two N-coordenated sac , bit and two S-coordenated tsac ligand, from the square planar coordination geometry around the palladium (II) ion.
European Journal of Inorganic Chemistry, 2006
Treatment of the tetradentate (NN 0 N 0 N) N-alkylaminopyrazole ligands 3,6-dimethyl-1,8-(3,5-dimethyl-1-pyrazolyl)-3,6-diazaoctane (ddad) and 1,4-bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]piperazine (bedp) with [PdCl 2 (CH 3 CN) 2 ] in a 1:1 M/L ratio in acetonitrile produces [Pd 2 Cl 4 (L)] and [PdCl 2 (L)] (L = ddad and bedp). Treatment of the corresponding complex [PdCl 2 (L)] (L = ddad, bedp) in the presence of AgBF 4 in CH 2 Cl 2 /methanol (2:1) or NaBF 4 in acetonitrile gives [Pd(L)](BF 4 ) 2 . The Pd(II) complexes have been characterised by elemental analyses, conductivity measurements, IR and 1 H and 13 C{ 1 H} NMR spectroscopies when possible. The X-ray structure of the complex [Pd(ddad)]Cl 2 Á 3H 2 O has been determined. The Pd(II) is coordinated to the ddad ligand by two nitrogen atoms of pyrazolyl groups and two nitrogen atoms of the amine groups, in a slightly distorted square-planar geometry.
Synthesis, characterization, and DFT calculation of a Pd(II) Schi base complex
The 4-((E)-(2-((E)-2, 4-dihydroxybenzylideneamino) ethylimino) methyl) benzene-1,3-diol tetradentate ligand, H2 L, reacted with PdCl2 to produce the related complex. The complex was characterized by elemental analysis, infrared and electronic spectroscopy, thermogravimetric study, and molar conductance. Furthermore, the fully optimized geometries were calculated using the ADF 2009.01 package. Comparison between the calculated and experimental results covering molecular structures, assignment of fundamental vibrational modes, and thermodynamic properties were investigated. The optimized molecular geometries were compared with the experimental data obtained from X-ray data of a similar complex, which indicated that the theoretical results agree with the corresponding experimental values. The UV-Vis spectrum of the compound was also recorded and some properties, such as HOMO and LUMO energies and max , were determined using DFT (PW91) method. The absorption wavelengths were compared with the experimental data.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2018
Binuclear palladium(II) complexes with metal-metal (d 8-d 8) bonding interaction were synthesized by reactions of the 1-methyl-1H-1,2,3,4-tetrazole-5-thiol (Hmtzt) or a mixture of Hmtzt and 1,3propanediamine (1,3-pda) ligands. Complex [Pd 2 (μ-mtzt) 4 ].2CH 3 CN (1) was synthesized by the reaction of Pd(OAC) 2 with Hmtzt dissolved in acetonitrile and complex [Pd 2 (μ-mtzt) 2 (mtzt) 2 (1,3-pda)](2) was synthesized by reaction of a mixture of Hmtzt and 1,3-propanediamine (dissolved in methanol) with PdCl 2 (dissolved in acetonitrile) and were identified through elemental analysis, IR, UV-Vis, 1 H NMR, luminescence spectroscopy as well as single-crystal X-ray diffraction method. A single-crystal of complex 1 shows that two Pd(II) centers are linked together by four bridging tetrazole ligands providing a paddle wheel-like arrangement. Also a crystal structure of complex 2 shows that this complex possesses a symmetric structure in which one Pd atom is tetra-coordinated by four sulfur atoms to forms PdS 4 and other Pd atom is tetra-coordinated by four nitrogen to forms PdN 4 coordination sphere. Density functional theory (DFT) was performed in this study for the Hmtzt ligand and binuclear palladium(II) complexes (1) and (2). The DFT calculation shows Pd II-Pd II bond lengths of 2.831 and 3.086 Å in complex 1 and 2, respectively which are close to the observed bond lengths of 2.802(11) and 3.0911(17) Å from singlecrystal X-ray structure. The optimized geometry of the complexes is shown good agreement by X-ray data. Structural properties and molecular descriptors including bond lengths, bond angles, chemical hardness, dipole moment, HOMO-LUMO energy levels, electron transfer were analyzed The IR spectroscopy was performed using VEDA4 software and UV-Vis spectra were analyzed using timedependent density functional theory (TD-DFT) method. The theoretical and experimental data were also compared with each other.
Inorganica Chimica Acta, 2006
Reaction of the N-alkylaminopyrazole (NN 0 N) ligands bis [(3,5-dimethyl-1-pyrazolyl)methyl]ethylamine (bdmae) and bis[(3,5dimethyl-1-pyrazolyl)methyl]isopropylamine (bdmai) with [PdCl 2 (CH 3 CN) 2 ] in a 1:1 M/L ratio in CH 2 Cl 2 produces cis-[PdCl 2 (NN 0 N)] (NN 0 N = bdmae (1), bdmai (2)). The solid state structure of complex 1 was determined by X-ray diffraction studies. The bdmae ligand is coordinated through the two N pz atoms to the metal atom, which completes its coordination with two chlorine atoms in a cis disposition.
Polyhedron, 2009
Mononuclear palladium(II) complexes containing a pyrazole-thioether ligand, with general formula trans-[Pd(X) 2 (bddo)] (X = CN À (1), SCN À (2) or N 3 À (3); bddo = 1,8-bis(3,5-dimethyl-1-pyrazolyl)-3,6dithiaoctane), have been prepared. Similar reactivity carried out with pyridine or triphenylphosphine has been assayed. When pyridine is used, a mixture of [Pd(bddo)(py) 2 ](BF 4 ) 2 ([4](BF 4 ) 2 ) and [Pd(bddo)](BF 4 ) 2 is obtained. When triphenylphosphine is used, only [Pd(bddo)](BF 4 ) 2 is obtained. The complexes have been characterised by elemental analyses, conductivity measurements, IR and NMR spectroscopies. X-ray crystal structure of trans-[Pd(SCN) 2 (bddo)] (2) is presented. In this complex the metal atom is coordinated by the two azine nitrogen atoms of the pyrazole rings and two SCN À anions in trans disposition.
Inorganic Chemistry, 2003
Department of Chemistry, h h e n g Teachers University, h h e n g , 252059 Chlorodibenzyltin(IV) complex with dithiomorphoIin& mate ligand was synthesiZea by the reaction of d i i t i n dichloride with dithiomrpholinocarbamate in 1 : 1 stoichiomel q. 'he complex was characterized by elementary analysis, UV, IRand'HNMRspedm. 'hecrystalstructurewasdetermined by X-ray single crystal diffraction study. 'he crystallo-0.8723(2) nm, b=1.099(2) nm, c =1.1036(3) MI, a = 86.498(4)", B = 8 9. 6 9 7 (5) " , y = 82.807(5)", Z = 2 , V = 1.0479(4) nrd, D, = 1.580 P/m-', p = 1.553 mm-', F(000) =500, R1 = 0. M 2 , wR2 = 0.0974. 'be crystal consists of discrete molecules containing five-coordinate tin atom in a distorted tigod bipy-ramidai cwfiguration. 'Ihe m o l e c u l e s are packed in the unit cell in one-dimensional chain structure through a weak interaction between the chlorine atom and sulfur atom, the sulfur atom and one of the s u h r s of an adjacent molecule. graphic data BE fouom: triclini~, s p a~e group pi, u = Key~ordS chlorodibenzyltin(I S ') complex, dithiornorpholinocarbarnate, crystal structure, S.
Solid State Sciences, 2010
The binuclear transition metal dialkynyl bridged Pd(II) complexes trans,trans-[ClPd(PBu 3 ) 2 eC^Ce C 6 H 4 eC 6 H 4 eC^CePd(PBu 3 ) 2 Cl] and trans,trans-[CH 3 OCeSePd(PBu 3 ) 2 eC^CeC 6 H 4 eC 6 H 4 eC^CePd (PBu 3 ) 2 eSeCOCH 3 ] were synthesized and investigated by X-ray Photoemission (XPS) and X-ray Absorption (XAS) spectroscopies. XPS measurements lead to assess that the thiolate terminal group does not affect dramatically the electronic structure of the transition metal, and as a consequence the two complexes are expected to possess analogous molecular structure. XAS data analysis suggested a squareplanar geometry around the palladium center in both binuclear compounds.