共查询到20条相似文献,搜索用时 15 毫秒
1.
Di-μ-chlorobis(2-methyl-2-methoxy-3-t-butylthiopropyl)dipalladium(II) reacted with bis(1,3-diphenyl-2-imidazolidinylidene) to afford a new chlorobridged carbene complex [{PdCl(did)}2] (did 1,3-diphenyl-2-imidazolidinyl-idenato,2-C,2′-C) in 46.2% yield, which has a cyclopalladated chelate structure involving a Pd—carbene and a Pd—aryl bond; new carbene complexes, [{PdBr(did)}2], [{Pd(CH3COO)(did)}2], [Pd(acac)(did)], and [PdCl(did)Q] (Q 4-MePy, P[OCHMe2]3) were also prepared from [{PdCl(did)}2]. 相似文献
2.
Yan Gao Saimeng Zhang Xiaoguang Li Shuyao Jiang Yajing Yang Xiaohong Chang 《应用有机金属化学》2020,34(2):e5330
Salicylaldimine-bridged dinuclear cyclopalladated complexes were synthesized by the reactions of cyclopalladated chloro dimers [Pd{(4-R)C6H3CH=N-C6H3–2,6-i-Pr2}(μ-Cl)]2 (R = H; OMe) with salen-based bridging ligands. The complexes were characterized by FTIR, NMR spectroscopy, elemental analysis and X-ray crystallography. The binding interaction of cyclopalladated complexes to bovine serum albumin (BSA) was investigated by UV–vis, fluorescence and synchronous fluorescence spectroscopy. The experimental results showed that these Pd (II) complexes could bind to BSA with high affinity and quench its intrinsic fluorescence by a static or combined process. Also the interaction of Pd complexes with BSA affected the conformation of the tryptophan and tyrosine residues. 相似文献
3.
《Journal of Coordination Chemistry》2012,65(16):2584-2589
The chloro-bridged dimer [Pd(μ-Cl)(C6H4CH2NH2-κ2-C,N)]2 reacts with PPh2Et, P(p-tolyl)3, AsPh3, piper (piper =?C5H10N) and Py in dichloromethane at room temperature for 24 h in a one-to-two molar ratio and undergoing bridge-splitting reactions to give [PdCl(C6H4CH2NH2–κ2-C,N)L] (L =?PPh2Et (1a), P(p-tolyl)3 (1b), AsPh3 (1c), piper (1d), C6H4CH2NH2 (3e) and Py (1f)). Complex 1f in THF at room temperature reacts with a stoichiometric amount of TlTfO (thallium triflate, TfO=CF3SO3) and Py (molar ratio 1 : 1 : 1) to afford [Pd(C6H4CH2NH2)(Py)2]TfO (2). Infrared and NMR spectroscopies allow unambiguous characterization of these products. 相似文献
4.
Santana MD García-Bueno R García G Sánchez G García J Pérez J García L Serrano JL 《Dalton transactions (Cambridge, England : 2003)》2011,40(14):3537-3546
The direct reaction between the hydroxo-complexes [{Pd(μ-OH)(C^N)}(2)] and protonated S^N-donor ligands to yield new dinuclear cyclometallated palladium(ii) complexes containing -NCS- bridging heterocyclic thionates of general formula [{Pd(μ-N^S)(C^N)}(2)] (C^N = 2-(2-pyridyl)phenyl (Phpy) I; = 7,8-benzoquinolyl (Bzq) II; N^S = pyrimidine-2-thionate (Spym) 1, benzoimidazolidine-2-thionate (Sbimid) 2, 1-methylimidazoline-2 thionate (Smeimid) 3) is described. The related mononuclear complexes [Pd(N^S)(C^N)] N^S = 2-aminothiophenolate (Atph) 4) were prepared in a similar way. Photophysical properties were investigated together with those of complexes with related ligands pyridin-2-thionate (Spy) 5 and pyrrole-2-carboxaldehydate (2-pcal) 6. All the compounds absorb intensely below 300 nm via(1)LC transitions located in Bzq or Phpy ligands, and display additional low energy absorptions of mixed (1)MLCT-(1)LC character. In the solid state diffuse reflectance UV-vis spectra, the differences are notable for dinuclear complexes. The complexes under study are quite unusual in terms of luminescence behaviour, since most of them are emissive in solution at room temperature and all display intense emissions in frozen CHCl(3) solution, but also in the solid state at 298 and 77 K. Emission quantum yields are in the range 2.52-0.14%, similar to that of related complexes. Structural characterisation by X-ray diffraction of complexes II3 and II6 confirmed the proposed formula. 相似文献
5.
Teresa Pugliese Nicolas Godbert Massimo La Deda Iolinda Aiello Mauro Ghedini 《Chemical physics letters》2005,410(4-6):201-203
The electrochemistry and the optical absorption properties of a series of cyclopalladated complexes are reported. Variation of the cyclometallated ligand has been performed (azobenzene, 2-phenylpyridine and benzo[h]quinoline) as well as variation of the ancillary ligand (acetylacetone and hexafluoroacetylacetone). Results have confirmed that the LUMO energy levels of these complexes is mainly distributed on the cyclometallated ligand. High electronegativity of the fluorinated groups has a weak influence on the electrochemical and absorption properties of the complexes, except for the benzo[h]quinoline for which its planar and comparatively more aromatic character lead to a partial delocalisation of the LUMO energy level. 相似文献
6.
Subrata Maity Ramkrishna Roy Chittaranjan Sinha Wen-Jyh Sheen Kaliyamoorthy Panneerselvam Tian-Huey Lu 《Journal of organometallic chemistry》2002,650(1-2):202-209
Binuclear chloro-bridged cyclopalladated azobenzenes [Pd(A)Cl]2 (A=ortho-metallated azobenzene or its derivatives) have been reacted with aqueous (aq.) AgNO3 followed by the addition of 2-hydroxypyridine (2-PyOH; donor centres of deprotonated form abbreviated N,O)/2-mercaptopyridine (2-PySH; donor centres of deprotonated form abbreviated N,S) in presence of Et3N to synthesise bridged dinuclear compound [Pd(A)(μ-N,O)]2–[Pd(A)(μ-N,S)]2. The compositions of the complexes have been established by elemental analyses, IR, UV–vis, 1H and 13C-NMR spectral data. The structural confirmation has been carried out by X-ray crystallography. The structures show anti-symmetric metallacycle in the dimer and N,O/N,S bridging arrangement. The dimer [Pd(A1)(μ-N,X)]2 shows strong PdPd interaction (A1=2-(phenylazo)benzene). The coordination mode in [Pd(A1)(μ-N,O)]2 shows trans pyridine-N to Pd---N(azo) bond while in [Pd(A1)(μ-N,S)]2 pyridine-N is trans to the Pd---C bond. The square planes are convergent towards heterocyclic bridging side. 相似文献
7.
A series of palladium complexes bearing monodentate and bidentate ligands were applied in the Suzuki reaction of aryl halides and the Heck reaction of styrene with phenylboronic acid. The complexes were found to be effective catalysts for these reactions affording the cross-coupled products in moderate to excellent yields. 相似文献
8.
Concepción Gómez-Vaamonde Amparo Alvarez-Valdés María del Carmen Navarro-Ranninger José R. Masaguer 《Transition Metal Chemistry》1984,9(2):52-54
Summary The synthesis and identification of the compoundstrans-bis(2-aminopyridine)dichloropalladium(II) and tetrakis(2-aminopyridine)palladium(II) chloride are described. The infrared spectra are discussed, particularly the metal-halogen and metal-ligand vibrations. Thermal decomposition was studied by differential thermal analysis (DTA) and thermogravimetry (TG). 相似文献
9.
Joan Albert Jaume Granell Mercè Font-Bardia 《Journal of organometallic chemistry》2005,690(2):422-429
2-Phenylaniline reacted with Pd(OAc)2 in toluene at room temperature for 24 h in a one-to-one molar ratio and with the system PdCl2, NaCl and NaOAc in a 1 (2-phenylaniline):1 (PdCl2):2 (NaCl):1 (NaOAc) molar ratio in methanol at room temperature for one week to give the dinuclear cyclopalladated compounds (μ-X)2[Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}]2 [1a (X = OAc) and 1b (X = Cl)] in high yield. Moreover, the reaction between 2-phenylaniline and Pd(OAc)2 in one-to-one molar ratio in acid acetic at 60 °C for 4 h, followed by a metathesis reaction with LiBr, allowed isolation of the dinuclear cyclopalladated compound (μ-Br)2[Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}]2 (1c) in moderate yield. A parallel treatment, but using monodeuterated acetic acid (DOAc) as solvent in the cyclopalladation reaction, allowed isolation of a mixture of compounds 1c, 1cd1 [Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4](μ-Br)2[Pd{κ2-N2′,C1-2-(2′-NH2C6H4)-3-d-C6H3] and 1cd2 (μ-Br)2[Pd{κ2-N2′,C1-2-(2′-NH2C6H4)-3-d-C6H3}]2 in moderate yield and with a deuterium content of ca. 60%. 1a and 1b reacted with pyridine and PPh3 affording the mononuclear cyclopalladated compounds [Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}(X)(L)] [2a (X = OAc, L = py), 2b (X = Cl, L = py), 3a (X = OAc, L = PPh3) and 3b (X = Cl, L = PPh3)] in a yield from moderate to high. Furthermore, 1a reacted with Na(acac) · H2O to give the mononuclear cyclopalladated compound 4 [Pd{κ2-N2′,C1-2-(2′-NH2C6H4)C6H4}(acac)] in moderate yield. 1H NMR studies in CDCl3 solution of 2a, 2b, 3a, 3b and 4 showed that 2a and 3a presented an intramolecular hydrogen bond between the acetato ligand and the amino group, and were involved in a dynamic equilibrium with water present in the CDCl3 solvent; and that the enantiomeric molecules of 2b and 4 were in a fast exchange at room temperature, while they were in a slow exchange for 2a, 3a and 3b. The X-ray crystal structures of 3b and 4 were determined. 3b crystallized in the triclinic space group with a = 9.9170(10), b = 10.4750(10), c = 12.0890(10) Å, α = 98.610(10)°, β = 94.034(10)° and γ = 99.000(10)° and 4 in the monoclinic space group P21/a with a = 11.5900(10), b = 11.2730(10), c = 12.2150(10) Å, α = 90°, β = 107.6560(10)° and γ = 90°. 相似文献
10.
11.
Matsuo Nonoyama 《Journal of organometallic chemistry》1978,154(2):169-174
Palladium(II) complexes of biacetylmonoxime arylhydrazones (HL, aryl = phenyl, o-, m-, and p-tolyl, p-chloro- and p-nitrophenyl) and biacetylmonoxime N′-methyl-phenylhydrazone (HL′) have been prepared and characterized. The hydrazomines, HL and HL′, are coordinated through oxime- and hydrazone-nitrogen atoms as a bidentate ligand in the complexes [PdX2(HL or HL′)] (X = halogen atom) formed under neutral conditions. Under basic conditions the deprotonated complexes [PdX(L or L′)] are obtained. Deprotonation occurs at the oxime group of HL′ and the ligand remains coordinated through oxime- and hydrazone-nitrogen atoms. The other hydrazoximes (HL) are cyclopalladated at the ortho position of the benzene rings and act as an NNC terdentate ligand in the deprotonated complexes [PdXL]. 相似文献
12.
Treatment of calcium bromide with 3,5-di-tert-butylpyrazolatopotassium (2 equiv) in tetrahydrofuran afforded Ca(tBu2pz)2(THF)2 (69%). The reaction of this compound with pyridine (3 equiv), tetramethylethylenediamine (TMEDA, 1 equiv), N,N,N',N',N"-pentamethyldiethylenetriamine (PMDETA, 1 equiv), triglyme (1 equiv), and tetraglyme (1 equiv) yielded Ca(tBu2pz)2(py)3 (51%), Ca(tBu2pz)2(TMEDA) (74%), Ca(tBu2pz)2(PMDETA) (50%), Ca(tBu2pz)2(triglyme) (73%), and Ca(tBu2pz)2(tetraglyme) (57%), respectively. Treatment of the tetrahydrofuran adduct of Ca(Me2pz)2, generated in situ, with PMDETA (1 equiv), triglyme (1 equiv), and tetraglyme (1 equiv) afforded Ca(Me2pz)2(PMDETA) (65%), Ca(Me2pz)2(triglyme) (54%), and Ca(Me2pz)2(tetraglyme) (40%), respectively. The X-ray crystal structures of Ca(tBu2pz)2(py)3, Ca(tBu2pz)2(TMEDA), Ca(tBu2pz)2(PMDETA), Ca(tBu2pz)2(triglyme), and Ca(Me2pz)2(PMDETA) revealed six-, seven-, or eight-coordinate calcium centers with eta 2-pyrazolato ligands. Ca(tBu2pz)2(triglyme) sublimes at 160 degrees C (0.1 mmHg). The potential utility of these complexes as source compounds for chemical vapor deposition processes is discussed. 相似文献
13.
Kwon HY Lee SY Lee BY Shin DM Chung YK 《Dalton transactions (Cambridge, England : 2003)》2004,(6):921-928
Addition of primary amines to N-[2-(diphenylphosphanyl)benzoyloxy]succinimide affords 2-diphenylphosphanylbenzamides, Ph2PC6H4C(O)NHR (R = C(CH3)3, 3; R = H, 4; R = CH2CH2CH3, 5; R = CH(CH3)2, 6). Addition of NiCl(eta3-CH2C6H5)(PMe3) to the deprotonated potassium salts of the amides and subsequent treatment of two equivalents of B(C6F5)3 to the resulting products furnishes eta3-benzyl zwitterionic nickel(II) complexes, [Ph2PC6H4C(O)NR-kappa2N,P]Ni(eta3-CH2C6H5) (R = C6H5, 9; R = C(CH3)3, 10; R = H, 11; R = CH2CH2CH3, 12; R = CH(CH3)2, 13). Solid structures of 9, 11, 13 and the intermediate eta1-benzyl nickel(II) complexes, [Ph2PC6H4C(O)NR-kappa2N,P]Ni(eta1-CH2C6H5)(PMe3) (R = C6H5, 7; R = C(CH3)3, 8) were determined by X-ray crystallography. When ethylene is added to the eta3-benzyl zwitterionic nickel(II) complexes, butene is obtained by the complexes 9-12 but complex 13 provides very high molecular-weight branched polyethylene (Mw, approximately 1300000) with excellent activity (up to 5200 kg mol-1 h-1 at 100 psi gauge). 相似文献
14.
Matsuo Nonoyama 《Transition Metal Chemistry》1987,12(1):1-3
Summary 2-(1-Pyrrolyl)pyrimidine(Hprpm) is cyclopalladated with lithium tetrachloropalladate in methanol in the presence of sodium acetate to give PdCl(prpm). This complex reacts with dimethylsulfoxide(dmso), pyridine(py). tri-n-butylphosphine(PBu3), tri-p-tolylphosphine(Ptol3), triphenylarsine(AsPh3), and acetylacetone(Hacac) to give PdCl(prpm)L (L=dmso, py, PBu3, Ptol3, AsPh3) and Pd(prpm)(acac), respectively. These complexes were characterized spectroscopically. The deprotonated ligand, prpm, is cyclopalladated and coordinated through pyrimidine-N and pyrrole-2C atoms to form a five membered palladaheterocycle. 相似文献
15.
Diorganohydrazido(2-) complexes of tungsten (L)Cl4W(NNR2) [R2=Me2, Ph2, -(CH2)5-; L=CH3CN, pyridine] were synthesized by reacting the corresponding 1,1-diorganohydrazine with WCl6, followed by reaction with acetonitrile or pyridine. Crystallographic structure determination of (CH3CN)Cl4W(NNMe2) and (CH3CN)Cl4W(NNPh2) allows a comparison of the structural features of the diorganohydrazido(2-) functionality with varying substituents. Mass spectrometry, thermogravimetric analysis, and preliminary chemical vapor deposition experiments were performed to determine the viability of these complexes as single-source precursors for deposition of WNx and WNxCy films. 相似文献
16.
17.
Synthesis, characterization, and applications in Heck and Suzuki coupling reactions of amphiphilic cyclopalladated ferrocenylimines 总被引:1,自引:0,他引:1
Bing Mu Tiesheng Li Wenjian Xu Guoliang Zeng Pingping Liu Yangjie Wu 《Tetrahedron》2007,63(46):11475-11488
A series of novel amphiphilic ferrocenylimines and their cyclopalladated complexes of general formula [Fe(η5-C5H5)(η5-C5H4CR1NR2)] (R1=H, R2=C12H25-n4a, R1=H, R2=C16H33-n4b, R1=CH3, R2=C12H25-n4c, R1=CH3, R2=C16H33-n4d), [PdCl{[(η5-C5H5)]Fe[(η5-C5H3)CR1NR2]}]2 (5a-d), [PdCl{[(η5-C5H5)]Fe[(η5-C5H3)-CR1NR2]}(PPh3)] (6a-d), were prepared and characterized by 1H NMR, 13C NMR, 31P NMR, IR, HRMS, and elemental analysis. The crystal structures of 5c,d were determined by X-ray crystallography. These amphiphilic cyclopalladated complexes are thermally stable and insensitive to oxygen and moisture. The redox properties of 4a-d, 5a-d, 6a-d were also investigated using cyclic voltammetric technique. Compounds 5a-d, 6a-d displayed good activity in the Heck reaction of a variety of aryl halides with ethyl acrylate or styrene and the Suzuki-Miyaura cross-coupling reaction of aryl bromides with phenylboronic acid in bulk solution. They are also suitable for formation of Langmuir-Blodgett (LB) films. 相似文献
18.
《Journal of organometallic chemistry》2006,691(1-2):255-260
A new heteroannular cyclopalladated ferrocene derivative [PdCl{C5H4FeC5H4CH2NCH–C4H3S}(PPh3)] (6) was synthesized and characterized by IR, 1H NMR, 13C NMR, high resolution mass spectroscopy, and its molecular structure was further confirmed by X-ray crystal structure determination. According to the crystal structure, the palladium atom is bound to the unsubstituted Cp ring, showing the four-coordinate structure typical of palladium complexes. A preliminary application of these novel cyclopalladated complexes in Mizoroki–Heck reaction is also to be demonstrated in this paper. 相似文献
19.
Sandra C. Zinner Wolfgang A. Herrmann Fritz E. Kühn 《Journal of organometallic chemistry》2008,693(8-9):1543-1546
New chiral and non-chiral rhodium(I)–NHC complexes were synthesized. The first attempt by deprotonation of an imidazolinium salt with KOtBu and reaction with [Rh(COD)Cl]2 leads to the corresponding rhodium(I) complex. Due to the basic conditions during the reaction a loss of chirality occurs. An alternative transmetallation reaction with a silver(I)–NHC complex yields the desired rhodium(I)–NHC complex under retention of chirality. Both Rh complexes were fully characterized by analytical methods. 相似文献
20.
Mohammad El-khateeb Taghreed M. A. Jazzazi Helmar Görls Tareq M. A. Al-Shboul Matthias Westerhausen 《Transition Metal Chemistry》2011,36(1):29-33
The cyclopentadienyl ruthenium complexes CpRuL2SCO-het (Cp = η5-C5H5; L2 = 2PPh3 (1), dppe (2)) bearing heterocyclic thiocarboxylate ligands have been synthesized from the reaction of CpRuL2SH with heterocyclic acid chlorides (ClCO-2-C4H3S (a); ClCO-2-C4H3O (b); ClCO-1-C4H8N (c)). Bubbling of CO gas through a THF solution of (1) produced the mixed carbonyl–phosphine complexes CpRu(PPh3)(CO)SCO-het (3) with high yields. Complexes (1)-(3) were characterized by spectroscopic methods (i.r., 1H-n.m.r., 31P-n.m.r.) and elemental analysis. The molecular structure of CpRu(PPh3)2SCO-2-C4H3S (1a) verifies that the thiocarboxylate ligands bind via the sulfur atom (Ru–S = 2.406(2) Å). 相似文献