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1.
Palladium-catalyzed reactions of aryl bromides with various olefins involving Pd(II)/diazabutadiene (DAB-R) systems have been investigated. The scope of a coupling process using Pd(II) sources and an α-diimine as ligand in the presence of Cs2CO3 as base was tested using various substrates. The Pd(OAc)2/DAB-Cy (1, DAB-Cy=1,4-dicyclohexyl-diazabutadiene) system presents the highest activity with respect to electron-neutral and electron-deficient aryl bromides in coupling with electron rich olefins. The synthesis and X-ray characterization of a Pd(II)-diazabutadiene ligand is reported. Extensive optimization experiments showed that another Pd(II) source, Pd(acac)2 (acac=acetylacetonate), proved to activate aryl bromides at high temperatures, low catalyst loadings when the appropriate concentration of nBu4NBr additive was employed. The effect of the DAB-Cy ligand is important at very low catalyst loadings and high temperatures. Pd(acac)2 and Pd(acac)2/DAB-Cy precatalysts were very effective for the arylation of various olefins with aryl bromides with respect to reaction rate, catalyst loadings, and functional group tolerance.  相似文献   

2.
The mechanism of the reactions of aryl/heteroaryl halides with aryl Grignard reagents catalyzed by [FeIII(acac)3] (acac=acetylacetonate) has been investigated. It is shown that in the presence of excess PhMgBr, [FeIII(acac)3] affords two reduced complexes: [PhFeII(acac)(thf)n] (n=1 or 2) (characterized by 1H NMR and cyclic voltammetry) and [PhFeI(acac)(thf)]? (characterized by cyclic voltammetry, 1H NMR, EPR and DFT). Whereas [PhFeII(acac)(thf)n] does not react with any of the investigated aryl or heteroaryl halides, the FeI complex [PhFeI(acac)(thf)]? reacts with ArX (Ar=Ph, 4‐tolyl; X=I, Br) through an inner‐sphere monoelectronic reduction (promoted by halogen bonding) to afford the corresponding arene ArH together with the Grignard homocoupling product PhPh. In contrast, [PhFeI(acac)(thf)]? reacts with a heteroaryl chloride (2‐chloropyridine) to afford the cross‐coupling product (2‐phenylpyridine) through an oxidative addition/reductive elimination sequence. The mechanism of the reaction of [PhFeI(acac)(thf)]? with the aryl and heteroaryl halides has been explored on the basis of DFT calculations.  相似文献   

3.
Bridged N,N′-substituted bisbenzimidazolium bromide salts (L1, L2, and L3) were synthesized and fully characterized. Reactions of palladium acetate with L1, L2, and L3 afforded corresponding new bridged bis(N-heterocyclic carbene)palladium(II) complexes (C1, C2, and C3) in high yields. The X-ray structure of complex C1 showed that the Pd(II) ion is bonded to the two carbon atoms of the bis(N-heterocyclic carbene) and two bromido ligands are in the cis position, resulting in a distorted square planar geometry. The three Pd(NHC)2Br2 complexes C1, C2, and C3 were evaluated in carbonylative Suzuki–Miyaura coupling reactions of aryl boronic acids with aryl halides and displayed high catalytic activity with low catalyst loading. The coupling reactions of aryl bromides were selective towards the carbonylation product at higher carbon monoxide pressure.  相似文献   

4.
Two equivalents of acetylacetonate (acac) have been successfully introduced into a monomeric tungsten(II) coordination sphere. With the tetracarbonyltriiodotungsten(II) anion as a precursor, the formation of a tungsten(II) bis(acac) tricarbonyl complex, W(CO)3(acac)2, 1, has been accomplished. The addition of PMe3 or PMe2Ph to tricarbonyl complex 1 formed tungsten(II)bis(acac)dicarbonylphosphine complexes 2a and 2b, respectively. Single-crystal X-ray diffraction studies of the parent tricarbonyl complex, 1, and dicarbonyl trimethylphosphine complex 2a confirmed seven-coordinate geometries for both complexes. Variable-temperature 1H and 13C{1H} NMR spectroscopy revealed fluxional behavior for these seven-coordinate molecules: rapid exchange of the three carbon monoxide ligands in 1 was observed, and movement of the phosphine ligand through a mirror plane in a C(S) intermediate species was observed for both 2a and 2b. Tricarbonyl complex 1 reacted readily with alkyne reagents to form bis(acac)monocarbonylmonoalkynetungsten(II) complexes 3a (PhC(triple bond)CH) and 3b (MeC(triple bond)CMe). Variable-temperature 1H NMR spectroscopy was used to probe rotation of the alkyne ligand in 3a and 3b. The introduction of two alkyne ligands was accomplished thermally using excess PhC(triple bond)CPh to form bis(alkyne) complex 4 which was characterized crystallographically, as well as by 1H and 13C NMR spectroscopy. The availability of W(CO)3(acac)2 as a source of the W(acac)2 d4 moiety lies at the heart of the chemistry reported here.  相似文献   

5.
Thermal reactions of the nickel(II) complexes, [Ni(m-bn or i-bn)2]X2 and [Ni(H2O)2(dl-bn)2]X2·n H2O, where m-bn, i-bn, and dl-bn are meso-2,3-butanediamine, 2-methyl-1,2-propanediamine, and dl-2,3-butanediamine, respectively, X is Cl?, Br?, I?, NO?3, or ClO?4, and n is 2 for bromide, and 0 for the others, were investigated in a solid phase before and after heating using thermal analyses (TG and DSC) and spectral and magnetic measurements. In the case of the chloride and bromide, the square planar bis(dl-bn) complexes obtained by dehydration of the respective diaqua complexes were transformed to the octahedral diacido bis(dl-bn) complexes upon further heating. The same structural transformation was observed in the thermal reactions of [Ni(m-bn)2](NO3)2 and [Ni(i-bn)2]Cl2. It was summarily recognized that such square planar-to-octahedral transformation was favored in the order dl-bn > i-bn > m-bn complexes in the respective halides, and it was a reversible thermochromism from yellow to blue. The changes in enthalpy of the reactions were endothermic and fell in the range of about 10–20 kJ mole?1. The possibility of such configurational change seems to be dependent mainly upon the ionic radius of the X anion, the orientation of two C-substituted methyl groups on butanediamines in the formation of the complexes, and the thermal stability of the complexes themselves.  相似文献   

6.
The synthesis, characterization, crystal structure and catalyst activity of the bidentate phosphine complex [1,2‐bis(diphenylphosphino)ethane]palladium(II) bromide, [PdBr2(dppe)], are presented. Treatment of 1,2‐bis(diphenylphosphino)ethane with palladium(II) bromide under mild conditions resulted in the compound in high yield and purity. The characterization of the synthesized compound was performed using spectroscopic methods, such as Fourier transform infrared and NMR, CHN analysis and X‐ray crystallography. The structure of the compound was slightly distorted square planar. This compound was found to work as an efficient catalyst for both Stille and Suzuki cross‐coupling reactions of various aryl halides with triphenyltin chloride and/or phenylboronic acid. Also, the catalyst could be recovered and reused several times without significant loss of its catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

7.
Two new mixed ligand complexes of copper(II) with acetylacetonate (acac), 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) belonging to the class of cytotoxic and antineoplastic compounds known as CASIOPEINAS® were synthesized and structurally characterized. Crystals of both complexes [Cu(acac)(bpy)(H2O)]NO3 · H2O (1), [Cu(acac)(phen)Br] (2) contain square pyramidal Cu(II) complex species. In frozen solution both compounds give well resolved EPR spectra with very similar parameters.  相似文献   

8.
Bis(acetylacetonate)alumo‐oxo‐tetraphenyldisiloxane‐metal(II) dihydrates [(acac)2Al(O–SiPh2–O–SiPh2–O)]2M(H2O)2 (M = Mg, Fe, Co, Ni) were obtained from the corresponding acetyl‐acetonate‐dihydrates (acac)2M(H2O)2 by reaction with the alumosiloxane [O–Ph2Si–O–SiPh2–O]4Al4(OH)4. These new compounds display two acac ligands at the aluminum atoms as well as disilatrioxy chains linking the two aluminum atoms forming a (Al–O–Si–O–Si–O)2 cycle (X‐ray structure analyses). Within this cycle the divalent metal ions M2+, to which two water molecules in trans positions are linked, are installed in almost planar MO4 coordination spheres. Using water free (acac)2Ni a different product forms: both reactants combine in a 2:1 ratio to yield [O–Ph2Si–O–SiPh2–O]4Al4(OH)2O(OH2)Ni2(acac)4. Here, three of the acac ligands were transposed to the aluminum atoms. The nickel atoms are in a distorted octahedral coordination mode from oxygen atoms of the ligands. When iron(III)tris(acetylacetonate) reacts with the alumosiloxane [O–Ph2Si–O–SiPh2–O]3Al2O(OH)Fe2(acac)3 was isolated, in which the two iron atoms still display one of the acac ligands. One of the aluminum atoms is in a tetrahedral oxygen environment, whereas the other is in the center of a trigonal bi‐pyramid formed of oxygen atoms either of the siloxane or of acac. The iron atoms have five‐ or sixfold coordination from oxygen atoms of siloxane, acac, hydroxide or oxide.  相似文献   

9.
Negishi cross-coupling reaction of organozinc compounds as nucleophiles with aryl halides has drawn immense focus for C−C bond formation reactions. In comparison to the well-established library of Pd complexes, the C−C cross-coupling of this particular approach is largely primitive with nickel-complexes. Herein, we describe the syntheses of Ni(II) complexes, [(MeBICAAC)2NiX2] (X=Cl ( 1 ), Br ( 2 ), and I ( 3 )) by employing the bicyclic (alkyl)(amino)carbene (MeBICAAC) ligand. The reduction of complexes 1 – 3 using KC8 afforded the two coordinate low valent, Ni(0) complex, [(MeBICAAC)2Ni(0)] ( 4 ). Complexes 1 – 4 have been characterized by spectroscopic techniques and their solid-state structures were also confirmed by X-ray crystallography. Furthermore, complexes 1 – 4 have been applied in a direct and convenient method to catalyze the Negishi cross-coupling reaction of various aryl halides with 2,6-difluorophenylzinc bromide or phenylzinc bromide as the coupling partner in the presence of 3 mol % catalyst. Comparatively, among all-pristine complexes, 1 exhibit high catalytic potential to afford value-added C−C coupled products without the use of any additive. The UV-vis studies and HRMS measurements of controlled stochiometric reactions vindicate the involvement of Ni(I)−NI(III) cycle featured with a penta-coordinated Ni(III)-aryl species as the key intermediate for 1 whereas Ni(0)/Ni(II) species are potentially involved in the catalytic cycle of 4 .  相似文献   

10.
Coordination compounds of ethylene trithiocarbonate (ETTC) with some Zn(II), Cd(II) and Hg(II) halides have been prepared, characterized and their infrared and Raman spectra recorded. The i.r. spectra in the range 4000-400 cm−1 suggest that the organic ligand is bonded to the metal ions through its exocyclic sulphur atom, whereas the far-i.r. and Raman spectra show that the complexes of the type HgX2(ETTC) (X = Cl, Br or I) possess a trans dimeric halogen-bridged structure. The Cd(II) and Zn(II) species are of the type MX2(ETTC)2 and they possess a pseudotetrahedral structure of C symmetry.  相似文献   

11.
Copper complexes of corroles have recently been a subject of keen interest due to their ligand non‐innocent character and unique redox properties. Here we investigated bis‐copper complex of a triply‐linked corrole dimer that serves as a pair of divalent metal ligands but can be reduced to a pair of trivalent metal ligands. Reaction of triply‐linked corrole dimer 2 with Cu(acac)2 (acac=acetylacetonate) gave bis‐copper(II) complex 2Cu as a highly planar molecule with a mean‐plane deviation value of 0.020 Å, where the two copper ions were revealed to be divalent by ESR, SQUID, and XPS methods. Oxidation of 2Cu with two equivalents of AgBF4 gave complex 3Cu , which was characterized as a bis‐copper(II) complex of a dicationic triply‐linked corrole dimer not as the corresponding bis‐copper(III) complex. In accord with this assignment, the structural parameters around the copper ions were revealed to be quite similar for 2Cu and 3Cu . Importantly, the magnetic spin–spin interaction differs depending on the redox‐state of the ligand, being weak ferromagnetic in 2Cu and antiferromagnetic in 3Cu .  相似文献   

12.
Andrei Gavryushin 《Tetrahedron》2006,62(32):7521-7533
A combination of diethyl phosphite-DMAP and Ni(II) salts forms a very effective catalytic system for the cross-coupling reactions of arylzinc halides with aryl, heteroaryl, and alkenyl bromides, chlorides, triflates, and nonaflates. The choice of solvent is quite important and the mixture of THF-N-ethylpyrrolidinone (NEP) (8:1) was found to be optimal. The reaction usually requires only 0.05 mol % of NiCl2 or Ni(acac)2 as catalyst and proceeds at room temperature within 1-48 h.  相似文献   

13.
A series of new ethylene-bridged bis(imidazolium) halides with various N-substitutions were synthesized. Complexation of these imidazolium halides with Pd(OAc)2 produced new Pd(II) ethylene-bridged bis(carbene) complexes. Crystallographic analyses of some of the new imidazolium salts and Pd(II) complexes were determined. Applications of these seven-member palladacycles in Suzuki and Heck coupling reactions produced comparable catalytic activities to those of six-member analogs.  相似文献   

14.
Microencapsulated copper(II) acetylacetonate was prepared and used in the aziridination of alkenes employing [N-(p-tolylsulfonyl)imino]phenyliodinane (PhINTs) as the nitrogen source. Microencapsulated copper(II) acetylacetonate [MC-Cu(acac)2] catalyst was reused for several cycles with consistent activity.  相似文献   

15.
Complexes of 2,4-pentanedione (acetylacetone, acac), [Cu(acac)2], [VO(acac)2] and [CO(acac)3], and the chromium(III) derivative of 3-methyl-2,4-pentanedione (methylacetylacetone, meac), [Cr(meac)3], the ligands bis(benzoylacetone)ethylenediimine and bis(salicylidene)ethylenediimine, and their cobalt(II), nickel(II) and copper(II) chelates were analysed by laser desorption mass spectrometry (LAMMA) and compared to electron impact (EI) results. The positive ion LAMMA spectra generally reveal mostly small fragments, although metal cationization peaks are seen for most complexes. Negative ion LAMMA produce carbon clusters and some structurally important fragments.  相似文献   

16.
The synthesis and characterization of two new complexes (IPr)Pd(acac)2 (1) and (IPr)Pd(acac)Cl (2) (IPr=(N,N'-bis(2,6-diisopropylphenyl)imidazol)-2-ylidene, acac=acetylacetonate) are described. Complex 2 can be prepared in a one-pot protocol in high yield. A study detailing the versatility of 2 to effectively catalyze a series of cross-coupling reactions is discussed.  相似文献   

17.
Experimental data on the synthesis of crystalline Cu, Cu2O, and CuO nanoparticles obtained earlier by the vapor-phase decomposition of copper(II) acetylacetonate (Cu(acac)2) were systematized and generalized. Studies were performed using a laminar flow reactor at atmospheric pressure within the ranges of precursor partial vapor pressure P prec = 0.06–44 Pa and reactor temperature from 432 to 1216°C. The decomposition of Cu(acac)2 was studied in an inert nitrogen atmosphere and in the presence of various reagents (water vapors, H2, O2, and CO). The composition of synthesized particles varied from pure copper to its oxides (Cu2O and CuO) depending on experimental conditions and used reagents. A semi-empirical kinetic model was proposed for describing the product dynamics. The hypothesis on the predominant role of copper dimers in a particles growth was stated. It was established that the composition of products is determined by the surface reactions on growing particles and is dependent on the ratio between the concentrations of the gaseous reagents. Calculated phase diagrams of the products of Cu(acac)2 decomposition in the presence of various reagents were in good agreement with experimental data. The proposed method of construction of the phase diagram of decomposition products can be employed for other systems. It was established that, upon the Cu(acac)2 decomposition in the presence of CO, carbon nano-onions were formed in addition to copper nanoparticles.Translated from Kolloidnyi Zhurnal, Vol. 67, No. 1, 2005, pp. 5–25.Original Russian Text Copyright © 2005 by Nasibulin, Shurygina, Kauppinen.  相似文献   

18.
We report the preparation of supported palladium(II) acetylacetonate, Pd(acac)2, coordinated by pendant acac groups, by reacting palladium acetate with acac‐functionalized doubly silica‐coated magnetic nanoparticles. The solid support consists of an amorphous silica‐coated (as magnetite protecting layer) magnetite core and a mesoporous silica shell. The magnetically separable palladium nanocatalyst is active for Suzuki cross‐coupling reaction of acyl halides with boronic acids. The catalyst is simply isolated from the reaction mixture that allows fast and efficient isolation of product and catalyst compared to traditional methods that generally make use of time‐ and solvent‐consuming procedures. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

19.
The binary system of bis(acetylacetonato)metal(II) [M(acac)2] and chloral induced the polymerization of chloral [M = Mn(II), Co(II), Mg(II), and Cu(II)], the ring-opening polymerization of styrene oxide [M = Co(II) and Mg(II)], and the radical polymerization of methyl methacrylate [M = Mn(II) and Co(II)]. The similar order of activity of M(acac)2 as the catalyst for the polymerization of chloral and for the aldol reaction of chloral with acetylacetone, the deactivation of the catalyst by the introduction of a substituent at the 3-position of M(acac)2, the presence of saturated β-diketone at the end of the polymer of chloral and that of styrene oxide, and the visible light spectral data supporting the formation of the β-ketoalcoholate intermediate in the binary system of Co(acac)2 and chloral are all experimental findings which suggest that M(acac)2 is subject to the aldol addition by chloral at the 3-position of the chelated acetylacetone and that the resultant β-ketoalcoholate is a common active species for these polymerizations.  相似文献   

20.
Novel red phosphorescent emitter bis(4-phenylquinazolinato-N,C2′) iridium(acetylacetonate) [(pqz)2Ir(acac)], bis(1-(1′-naphthyl)-5-methylisoquinolinato-N,C2′)iridium(acetylacetonate) [(1-mniq)2Ir(acac)] and bis(1-(2′-naphthyl)-5-methylisoquinolinato-N,C2′)iridium(acetylacetonate) [(2-mniq)2Ir(acac)] have been synthesized and fully characterized. The electronegative effect of (pqz)2Ir(acac) ligand shows almost the same influence as the extended π-conjugation effect of (2-mniq)2Ir(acac). Density functional theory (DFT) was applied to calculate the Kohn-Sham orbitals of HOMOs and LUMOs in the iridium complexes to illustrate the N(1) electronegative atom effect. Finally, lowest triplet state (T1) energies calculated by time-dependent DFT (TDDFT) were compared with the experimental electroluminescent data. The calculated data for the iridium complexes agreed fairly well with experimental data. Electroluminescent devices with a configuration of ITO/NPB/CBP:dopant/BCP/AlQ3/LiF/Al were fabricated. The device using (pqz)2Ir(acac) as a dopant showed deep-red emission with 1931 CIE (Commission International de L’Eclairage) chromaticity coordinates x = 0.70, y = 0.30.  相似文献   

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