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1.
Reaction of the dinuclear complex [Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}Cl]2 (1) with ligands (L = 4-picoline, sym-collidine) gave the six-membered palladacycles [Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}Cl(L)] (2). The complex 1 reacted with AgX (X = CF3SO3, BF4) and bidentate ligands [L–L = phen (phenanthroline), dppe (bis(diphenylphosphino)ethane), bipy(2,2′-bipyridine) and dppp
(bis(diphenylphosphino)propane)] giving the mononuclear orthopalladated complexes [Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}(L–L)] (3) [L–L = phen, dppe, bipy and dppp]. These compounds were characterized by physico-chemical methods, and the structure of
[Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}Cl(L)] (L = sym-collidine) was determined by single-crystal X-ray analysis. 相似文献
2.
Kyle N. W. Rozic Mahmood Azizpoor Fard Bahareh Khalili Najafabadi John F. Corrigan 《无机化学与普通化学杂志》2017,643(15):973-979
The manganese(II)‐palladium(II)‐sulfide complex [MnCl2(μ3‐S)2Pd2(dppp)2] ( 2 ) was prepared from the reaction of [PdCl2(dppp)] with [Li(N,N'‐tmeda)]2[Mn(SSiMe3)4] ( 2 ) in a 2:1 ratio under mild conditions. The new trimethylsilylthiolate complex [Pd(dppp)(SSiMe3)2] ( 3 ) was synthesized from the reaction of [Pd(dppp)(OAc)2] with two equivalents of Li[SSiMe3]; this was then used in a reaction with [Mn(CH3CN)2(OTf)2] to form the manganese(II)‐palladium(II)‐sulfide cluster [Mn(OTf)(thf)2(μ3‐S)2Pd2(dppp)2]OTf ( 4 ). 相似文献
3.
Shafqat Nadeem Muhammad Khawar Rauf Saeed Ahmad Masahiro Ebihara Syed Ahmed Tirmizi Sarfaraz Ahmed Bashir Amin Badshah 《Transition Metal Chemistry》2009,34(2):197-202
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 相似文献
4.
A new chelating radical ligand, IMMeBzIm (IMMeBzIm = 2-{2′-[(l′-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl)
and its copper(II) complex [Cu(IMMeBzIm)2(ClO4)]·(ClO4) have been prepared and characterized by IR, magnetic and single-crystal X-ray analysis. In the crystal structures, both
free IMMeBzIm and the complex crystallize in monoclinic space groups P2(1)/c and C2/c, respectively. The structure of IMMeBzIm consists of mononuclear molecules. In the complex, the coordination geometry around
copper is a distorted square pyramid, and the apical position is occupied by one oxygen atom of ClO4
− anion. A 1-D polymer is formed through intermolecular H-bond interactions. The variable-temperature magnetic susceptibility
of the free IMMeBzIm suggests weak antiferromagnetic coupling with J = −1.12 cm−1 where the spin Hamitonian is defined as Ĥ = −2 JŜ
1
Ŝ
2
between radical and radical. 相似文献
5.
The ortho-metalated complex [Pd(x){κ
2
(C,N)-[C6H4CH2NRR′ (Y)}] (2a–4a and 2b–3b) was prepared by refluxing in benzene equimolecular amounts of Pd(OAc)2 and secondary benzylamine [a, EtNHCH2Ph; b, t-BuNHCH2Ph followed by addition of excess NaCl. The reaction of the complexes [Pd(x){κ
2
(C,N)-[C6H4CH2NRR′ (Y)}] (2a–4a and 2b–3b) with a stoichiometric amount of Ph3P=C(H)COC6H4-4-Z (Z = Br, Ph) (ZBPPY) (1:1 molar ratio), in THF at low temperature, gives the cationic derivatives [Pd(OC(Z-4-C6H4C=CHPPh3){κ
2
(C,N)-[C6H4CH2NRR′(Y)}] (5a–9a, 4b–6b, and 4b′–6b′), in which the ylide ligand is O-coordinated to the Pd(II) center and trans to the ortho-metalated C(6)H(4) group, in an “end-on
carbonyl”. Ortho-metallation, ylide O-coordination, and C-coordination in complexes (5a–9a, 4b–6b, and 4b′–6b′) were characterized by elemental analysis as well as various spectroscopic techniques. 相似文献
6.
Alessandra Stevanato Antonio E. Mauro Adelino V. G. Netto 《Journal of Thermal Analysis and Calorimetry》2009,97(1):149-152
Synthesis, spectroscopic characterization and thermal analysis of the [Pd(dmba)(Cl)(iso)] (1), [Pd(dmba)(NCO)(iso)] (2), [Pd(dmba)(N3)(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 Pdo 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)(N3)(iso)] (3). 相似文献
7.
Vladimir P. Petrovi? Svetlana Markovi? Zorica D. Petrovi? 《Monatshefte für Chemie / Chemical Monthly》2011,17(1):141-144
Abstract
The mechanism of the formation of the active Pd(0) complex from trans-dichlorobis(diethanolamine-N)palladium(II) complex in the presence of strong base was investigated by using density functional theory (M06 method). Our investigation shows that in the basic environment trans-dichlorobis(diethanolamine-N)palladium(II) complex undergoes abstraction of the alcoholic proton, and coordination of alkoxide oxygen to palladium. The intermediate complex, in which hydrogen is coordinated to Pd, undergoes reductive elimination of HCl, yielding the catalytically active low ligated Pd(0) complex. 相似文献8.
《Journal of organometallic chemistry》2007,692(1-3):26-35
A series of heterodinuclear acylpalladium–cobalt complexes having a bidentate nitrogen ligand, L2(RCO)Pd–Co(CO)4 (L2 = bpy, R = Me (5), Ph (6); L2 = tmeda, R = Me (7), Ph (8); L2 = phen, R = Me (9), Ph (10)) are prepared by metathetical reactions of PdRIL2 with Na+[Co(CO)4]− followed by treatment with CO. These complexes are characterized by NMR and IR spectroscopies and elemental analyses, and the molecular structures of 6, 8, and 9 are determined by X-ray structure analysis. Geometry at Pd is essentially square planar and the Co atom is considered to have d10 tetrahedral structure, where cobalt(-I) anion coordinates to palladium(II) cation. Heterodinuclear organopalladium–cobalt complexes are shown to catalyze copolymerization of aziridines and CO under mild conditions. Reaction of (dppe)MePd–Co(CO)4 (1) with aziridine gives a cationic (aziridine)palladium(II) complex with [Co(CO)4]− anion, [PdMe(aziridine)(dppe)]+[Co(CO)4]− (13). 相似文献
9.
William Raven Irmgard Kalf Ulli Englert 《Acta Crystallographica. Section C, Structural Chemistry》2012,68(8):m223-m225
The enantiomerically pure title complex, [SP‐4‐4]‐(R)‐[2‐(1‐aminoethyl)phenyl‐κ2C1,N]chlorido(quinoline‐κN)palladium(II) acetone hemisolvate, [Pd(C8H10N)Cl(C9H7N)]·0.5C3H6O, crystallizes with four molecules of the organopalladium complex and two molecules of acetone in the asymmetric unit. This corresponds to a discrete hydrogen‐bonded aggregate and to the content of the unit cell in the space group P1. Pronounced pseudo‐inversion symmetry relates pairs of these objects in the asymmetric unit. 相似文献
10.
Murat Taş Seval Çamur Yalçın Kılıç 《Journal of Thermal Analysis and Calorimetry》2011,103(3):995-1000
The complexes were synthesized by the reaction between sodium salt of p-aminosalicylic acid (PAS) and Cu(II) for 1 and corresponding ethylenediamine (en) or its derivatives for 2–6. The complexes were characterized by using elemental analyses, FT-IR, UV–Vis, magnetic moment measurements, and thermal analyses
techniques. In complex 1[Cu2(PA)4(H2O)2], two Cu(II) ions were found as bridged by four μ-O:O′ p-aminosalicylato (PA) ligands, forming a cage structure, and two aqua ligands to form dinuclear square-pyramidal geometry
around Cu(II) ions. In the complexes 2–6, the PA (anionic form of p-aminosalicylic acid) coordinated to Cu(II) ions as monodentate manner by using its oxygen atom of deprotonated carboxylic
acid and ethylenediamine derivatives coordinated to the Cu(II) ions in bidentate manner to form mononuclear octahedral complexes
[Cu(PA)2(L)2] (L = ethylendiamine, N,N-dimethylethylendiamine, N,N′-dimethylethylendiamine, N,N,N′,N′-tetramethylethylendiamine, and 1,3-propanediamine, for complexes 2, 3, 4, 5, and 6, respectively). In all the complexes OH and NH2 groups of PA ligands were not coordinated to metals. 相似文献
11.
Darko P. Aanin Sneana Rajkovi Dora Molnar-Gabor Milos I. Djuran 《Monatshefte für Chemie / Chemical Monthly》2004,135(12):1445-1453
Summary. Hydrolytic reactions between various palladium(II) complexes of the type cis-[Pd(L)(H2O)2]2+ in which L is ethylenediamine (en), 1,2-propylenediamine (1,2-pn), isobutylenediamine (ibn), 1,2-diaminocyclohexane (1,2-dach), N-methylethylenediamine (Meen), N,N,N,N-tetramethylethylenediamine (Me4en), S-methyl L-cysteine (MeS-L-HCys), L-methionine (L-HMet), and 2,5-dithiahexane (dth) and dipeptide N-acetylated L-methionylglycine (MeCOMet-Gly) were studied by 1H NMR spectroscopy. The reactions were carried out in the pH range 2.0–2.5 and at 50°C. In all these reactions, palladium(II) complex bound to a methionine residue effects the regioselective cleavage of the amide bond involving the carboxylic group of methionine. We found that the rate of hydrolysis and mechanism of this reaction are strongly dependent from the nature of the chelate ligand L in palladium(II) complexes of the type cis-[Pd(L)(H2O)2]2+. 相似文献
12.
Darko P. A?anin Sne?ana Rajkovi? Dora Molnar-Gabor Milos? I. Djuran 《Monatshefte für Chemie / Chemical Monthly》2004,13(3):1445-1453
Hydrolytic reactions between various palladium(II) complexes of the type cis-[Pd(L)(H2O)2]2+ in which L is ethylenediamine (en), 1,2-propylenediamine (1,2-pn), isobutylenediamine (ibn), 1,2-diaminocyclohexane (1,2-dach), N-methylethylenediamine (Meen), N,N,N,N-tetramethylethylenediamine (Me4en), S-methyl L-cysteine (MeS-L-HCys), L-methionine (L-HMet), and 2,5-dithiahexane (dth) and dipeptide N-acetylated L-methionylglycine (MeCOMet-Gly) were studied by 1H NMR spectroscopy. The reactions were carried out in the pH range 2.0–2.5 and at 50°C. In all these reactions, palladium(II) complex bound to a methionine residue effects the regioselective cleavage of the amide bond involving the carboxylic group of methionine. We found that the rate of hydrolysis and mechanism of this reaction are strongly dependent from the nature of the chelate ligand L in palladium(II) complexes of the type cis-[Pd(L)(H2O)2]2+. 相似文献
13.
Camino Bartolomé Jose Miguel Martín-Alvarez Fernando Villafañe 《Journal of organometallic chemistry》2006,691(18):3862-3873
Halide abstraction from [Pd(μ-Cl)(Fmes)(NCMe)]2 (Fmes = 2,4,6-tris(trifluoromethyl)phenyl or nonafluoromesityl) with TlBF4 in CH2Cl2/MeCN gives [Pd(Fmes)(NCMe)3]BF4, which reacts with monodentate ligands to give the monosubstituted products trans-[Pd(Fmes)L(NCMe)2]BF4 (L = PPh3, P(o-Tol)3, 3,5-lut, 2,4-lut, 2,6-lut; lut = dimethylpyridine), the disubstituted products trans-[Pd(Fmes)(NCMe)(PPh3)2]BF4, cis-[Pd(Fmes)(3,5-lut)2(NCMe)]BF4, or the trisubstituted products [Pd(Fmes)L3]BF4 (L = CNtBu, PHPh2, 3,5-lut, 2,4-lut). Similar reactions using bidentate chelating ligands give [Pd(Fmes)(L-L)(NCMe)]BF4 (L-L = bipy, tmeda, dppe, OPPhPy2-N,N′, (OH)(CH3)CPy2-N,N′). The complexes trans-[Pd(Fmes)L2(NCMe)]BF4 (L = PPh3, tht) (tht = tetrahydrothiophene) and [Pd(Fmes)(L-L)(NCMe)]BF4 (L-L = bipy, tmeda) were obtained by halide extraction with TlBF4 in CH2Cl2/MeCN from the corresponding neutral halogeno complexes trans-[Pd(Fmes)ClL2] or [Pd(Fmes)Cl(L-L)]. The aqua complex trans-[Pd(Fmes)(OH2)(tht)2]BF4 was isolated from the corresponding acetonitrile complex. Overall, the experimental results on these substitution reactions involving bulky ligands suggest that thermodynamic and kinetic steric effects can prevail affording products or intermediates different from those expected on purely electronic considerations. Thus,water, whether added on purpose or adventitious in the solvent, frequently replaces in part other better donor ligands, suggesting that the smaller congestion with water compensates for the smaller M-OH2 bond energy. 相似文献
14.
Mathew Maria J. Selvakumar V.S. Raghunathan Tom Mathews K.S. Nagaraja 《Thermochimica Acta》2008,474(1-2):87-90
The reaction between the magnesium β-diketonate complex Mg(tmhd)2(H2O)2 and 1 equiv. of N,N,N′,N′-tetramethylethylenediamine (tmeda = Me2NCH2CH2NMe2) in hexane at room temperature yielded Mg(tmhd)2(tmeda). The standard enthalpy of sublimation (83.2 ± 2.3 kJ mol−1) and entropy of sublimation (263 ± 6.3 J mol−1 K−1) of Mg(tmhd)2(tmeda) were obtained from the temperature dependence vapour pressure, determined by adopting a horizontal dual arm single furnace thermogravimetric analyser as a transpiration apparatus. From the observed melting point depression DTA, the standard enthalpy of fusion (58.3 ± 5.2 kJ mol−1) was evaluated, using the ideal eutectic behaviour of Mg(tmhd)2(tmeda) as a solvent with bis(2,4-pentanedionato)magnesium(II), Mg(acac)2 as a non-volatile solute. 相似文献
15.
Karl-Heinz Lubert Markus Guttmann Lothar Beyer 《Journal of Solid State Electrochemistry》2002,6(8):545-552
The study of the electrode reactions of palladium(II) at non-modified carbon paste electrodes (CPEs) in chloride solution
has revealed the existence of a chloropalladate(II) complex at the electrode surface. The complex is formed during the application
of anodic potentials after preceding palladium deposition. In the present paper the electrode reactions of PdII at CPEs modified with some N′,N′-disubstituted derivatives of N-benzoylthiourea [as selective ligands for palladium(II)] are studied in chloride solution by cyclic voltammetry. Two reduction
peaks are observed in the cathodic scans recorded after deposition of palladium and anodization of the electrode. From the
results it is concluded that [in addition to the chloropalladate(II) complex, observed at the non-modified electrode] a second
palladium complex is formed at positive potentials. The formation of the palladium(II) complex of the N-benzoylthiourea derivatives by ligand exchange at the electrode surface is assumed. The ligand exchange itself occurs without
charge transfer across the electrode|solution interface; therefore, it cannot be detected electrochemically. After palladium
deposition and anodic treatment a pronounced "inverse" peak (i.e., an anodic peak in the cathodic scan) with peak currents
up to 100 μA is observed at about +0.8 V. Its peak current increases with the amount of deposited palladium and the number
of cycles. The reactions at the electrode surface are discussed. The results of the study reveal the existence of two different
surface complexes of palladium(II) at ligand-modified CPEs, but the surface reactions could not be elucidated in detail.
Electronic Publication 相似文献
16.
Bhattacharjee Rita Gayathri Virupaiah Gowda Nadur M.N. 《Transition Metal Chemistry》2004,29(3):320-328
The [Pd(cod)(cotl)]ClO4 complex (cod = cycloocta-1,5-diene; cotl = cyclooctenyl, C18H13
–) undergoes substitutions with new Schiff base ligands containing benzimidazole L [L = 2-(2-N-n-propylidenephenyl)benzimidazole (L1); 2-(2-N-i-propylidenephenyl)benzimidazole (L2); 2-(2-N-n-butylidenephenyl)benzimidazole (L3); 2-(2-N-i-butylidenephenyl)benzimidazole (L4)]. Facile displacement of cod by L occurs to produce complexes of the type [Pd(cotl)L]ClO4· nMe2CO (n= 0; L = L1, L2 or L3; n= 2, L = L4). Dihalobridge complexes of the type [Pd(cotl)X]2(X = Cl or Br) undergo halogen-bridge cleavage with L1–L4 to give mononuclear complexes of the type Pd(cotl)LX · nH2O (n= 2, X = Cl, L = L1; n= 0, X = Br, L = L1; n= 0, X = Cl, L = L2; n= 0, X = Cl or Br, L = L3; n= 0, X = Cl, L = L4; n= 2, X = Br, L = L4) and a binuclear complex [Pd(cotl)Br]2L2. The complexes were characterised by physical properties, i.r., 1H- and 13C-n.m.r. spectral techniques and by mass spectra. Probable structures have been proposed. 相似文献
17.
Maryam Tayebani Sandro Gambarotta Glenn P. A. Yap 《Angewandte Chemie (International ed. in English)》1998,37(21):3002-3005
A nitrogen center was abstracted from a pyrrolyl ring to form the dinuclear nitrido- and dienyl-bridged complex 1 during the reaction of [{(tmeda)NbIICl}2(μ-Cl)3Li(tmeda)] with the lithium salt of 2,5-dimethylpyrrole (tmeda=N,N,N′,N′-tetramethylethylenediamine). A second product from this reaction is the amido-carbene-hydride niobium complex 2 , which likewise forms under C−N bond cleavage. 相似文献
18.
Pritha Talukder Shyamapada Shit Heinrich N?th Matthias Westerhausen Alexander Nikolai Kneifel Samiran Mitra 《Transition Metal Chemistry》2012,37(1):71-77
A heterobimetallic cyano-bridged 1D coordination polymer of the composition [Ni(baepn)(μ-NC)Fe(CN)3(NO)(μ-CN)]n·3H2O has been synthesized by the reaction of nickel(II) nitrate hexahydrate, baepn (baepn = N, N′-bis(2-aminoethyl)-1,3-propanediamine), and sodium nitroprusside dihydrate in a methanol–water mixture. The complex was characterized
by physicochemical and spectroscopic methods. The crystal structure was established by single-crystal X-ray diffraction analysis.
It reveals cyano-bridged heterometallic chains consisting of alternating arrays of Ni(II) and Fe(II) atoms, both being embedded
in distorted octahedral environments. Low-temperature susceptibility measurements show the presence of weak antiferromagnetic
exchange interactions between paramagnetic Ni(II) centers (J = −0.46 cm−1) through long diamagnetic [Fe(CN)5(NO)]2− bridges. Spin state of the iron atom was established by 57Fe M?ssbauer spectroscopy. 相似文献
19.
Three new oxime‐based palladacycles, namely [Pd{C,N‐C6H4{C(Me)?NOH}‐2}(dppm)]ClO4 ( 1 ), [Pd2{C,N‐C6H4{C(Me)?NOH}‐2}2(dppe)2(μ‐dppe)](ClO4)2 ( 2 ) and [Pd{C,N‐C6H4{C(Me)?NOH}‐2}(dppmS2)]ClO4 ( 3 ), were synthesized by the reaction of dinuclear oxime complex [Pd{C,N‐C6H4{C(Me)?NOH}‐2}(μ‐Cl)]2 with different diphosphine ligands (dppm, dppe and dppmS2). The synthesized complexes were characterized using Fourier transform infrared, 31P NMR, 1H NMR and 13C NMR spectroscopic methods and elemental analyses, and their molecular structures were elucidated using X‐ray crystallography. The structure of 2 is worthy of note as it is the first oxime palladacycle where there are both bridging (P–) and chelating (P^P) dppe ligands, giving rise to a dinuclear complex. The palladium atom is in a five‐coordinate, square pyramidal P3NC environment, while in 3 the palladium atom is in a distorted square planar environment, coordinated by the oxime ligand and a chelating (S^S) dppmS2 ligand. These complexes were employed as efficient catalysts for the Suzuki–Miyaura cross‐coupling reaction of several aryl bromides with phenylboronic acid. The in vitro cytotoxicity of the compounds was also evaluated against human tumour cell lines (HT29, A549 and HeLa) using the MTT assay method. The results indicate that the dinuclear complex 2 has greater catalytic and anticancer activity in comparison with the mononuclear complexes 1 and 3 . 相似文献
20.
Yoshio Fuchita Kazuhiko Yoshinaga Tomoko Hanaki Hiroyuki Kawano Junko Kinoshita-Nagaoka 《Journal of organometallic chemistry》1999,580(2):2258
Cyclopalladation of mono-, di- and tribenzylamine has been investigated by reacting the corresponding amines with an equimolar amount of palladium(II) acetate (reaction i), or by heating the corresponding bis-amine complexes [Pd(O2CMe)2{(PhCH2)nNH3−n}2] (n=1, 2) (reaction ii). By the reaction i, all the three amines undergo cyclopalladation. However, in the case of the reaction ii, only the dibenzylamine complex [Pd(O2CMe)2{(PhCH2)2NH}2] has been converted into a cyclopalladated complex. The reactivity of the three benzylamines towards cyclopalladation has been discussed in terms of the co-ordinating ability influenced by the bulkiness around the nitrogen atom. Temperature-dependent 1H-NMR spectra are observed for mononuclear cyclopalladated complexes [Pd(O2CMe){C6H4CH2N(CH2Ph)2–C1, N}L] (L=PPh3, AsPh3) and are attributed to the dissociation of the nitrogen atom in the cyclopalladated chelate ring. A heteroleptic bis-cyclopalladated complex [Pd[C6H4CH2N(CH2Ph)2–C1, N](C6H4CH2NMe2–C1, N)] has also been prepared. X-ray crystallographic studies on [{Pd(O2CMe)[C6H4CH2N(CH2Ph)2–C1, N]}2] and [Pd[C6H4CH2N(CH2Ph)2–C1, N](C6H4CH2NMe2–C1, N)] have been reported. 相似文献