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Dong Mok Shin Seung Uk Son Bog Ki Hong Young Keun Chung Sung-Ho Chun 《Journal of molecular catalysis. A, Chemical》2004,210(1-2):35-46
A variety of neutral palladium(II) complexes [Pd(L–L)Cl2] containing 1,3-di(2-pyridyl)propane (1), 1,3-bis(2-pyridyl)-2-pentylpropane (2), 1,3-bis(2-pyridyl)-2-phenylpropane (3a), 1,3-bis(2-pyridyl)-2-tolylpropane (4), and 1,3-bis(2-pyridyl)-2-ferrocenylpropane (5) as chelate ligands (L–L) have been synthesized. The crystal structures of 1,3-diphenyl-2,4-di-pyridin-2-yl-butan-1-ol (3b), 5, [(2)PdCl2], [(4)PdCl2], and [(5)PdCl2] have been determined and show a square planar geometry at palladium(II). The neutral complexes were tested in the polymerization of norbornene and copolymerization of norbornene with norbornene derivatives. The complex bearing the pentyl group exhibited high reactivity to give up to 5.9×105 in molecular weight for the homopolymerization. When [(4)PdCl2] or [(5)PdCl2] was used as a catalyst, homopolymers insoluble at 150 °C in trichlorobenzene were obtained. However, copolymerization of norbornene with norbornene derivatives 8a–d catalyzed by [(4)PdCl2] gave soluble copolymers with molecular weights up to 5.1×105. 相似文献
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II 《Journal of organometallic chemistry》1993,450(1-2):263-267
Treatment of [Pd{CH2C(CH3)CH2}(Ph2PPy)Cl] (Ph2PPy = 2-(diphenylphosphino)pyridine) with cis-[Pd(tBuNC)2Cl2] in dichloromethane affords the mixed isocyanide-tertiary phosphine complex cis-[Pd(tBuNC)Ph2PPy)Cl2], in which the Ph2PPy is a monodentate P-donor, and [{Pd[CH2C(CH3)CH2]Cl}2]. The steric effects of the Ph2PPy bridging ligand in determining the reaction course is discussed. The complex cis-[Pd(tBuNC)(Ph2PPy)Cl2] was crystallographically characterized: P21/n, a = 15.143(2), b = 9.527(1), c = 17.517(4) Å, β = 113.96(1)°, V= 2309.4(7) Å3, Z = 4. The final R value was 0.044, Rw= 0.046 for the 3078 reflections with I > 3σ(I). 相似文献
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Two types of palladiu m(Ⅱ)-based metallacalixarenes[ML]2+and[ML2]2+have been synthesized through coordination-driven self-assembly from a series of flexible pyridine-bridged diimidazole ligands[2,6-bis((1 H-imidazol-1-yl)methyl)pyridine(L1),2,6-bis((1 H-benzo[d]imidazol-1-yl)methyl)pyridine(L2),2,6-bis((1 H-naphtho[2,3-d]imidazol-1-yl)methyl)pyridine(L3)],with palladium(II)-based building blocks[Pd(BF4)2(M1-BF_4)and(tmeda)Pd(NO3)2(M2-NO3)(tmeda=N,N,N',N'-tetramethyl-ethylenediamine)].All complexes were characterized by NMR spectroscopy(1H NMR and13C NMR),mass spectrometry(CSIMS,ESI-HRMS)and elemental analysis.The single crystal X-ray diffraction analysis of[M1L2_2](NO3)2,[M1L3_2](NO3)2,[M1L3_2](PF_6)_2 and[M~2 L3](NO3)2further confirmed the uniquely single bowl-shape and double bowl-shape structures.The anion binding properties within the metallacalixarenes as receptors were also investigated by NMR titration experiments in DMSO. 相似文献
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Thermal decomposition processes for cyclohexanediaminetetraacetic acid (CDTA-H4) complexes of palladium, [Pd(CDTA-H2)] and [Pd(CDTA-H4)Cl2]·2 HCl·2 H2O have been studied using TG—DTA techniques. Infrared spectroscopy and X-ray diffraction have been also used for the characterization of intermediate and final products. In the decomposition of the dichloro complex, chloride ions are released simultaneously to a ring closure reaction in which CDTA becomes tetradentate. For both compounds, the final product in the decomposition is PdO, as confirmed by the X-ray difraction pattern of a sample heated at 600°C. 相似文献
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Reactions of 2‐[1‐(3,5‐dimethylpyrazol‐1‐yl)ethyl]pyridine (L1) and 2‐[1‐(3,5‐diphenylpyrazol‐1‐yl)ethyl]pyridine (L2) with the [Pd (COD)Cl2] or [Pd (COD)MeCl] produced palladium (II) complexes [Pd( L1 )ClMe] ( 1 ), [Pd( L1 )Cl2] ( C2 ), [Pd( L2 )ClMe] ( 3 ), and [Pd( L2 )Cl2] ( 4 ) in quantitative yields. Solid state structures of complexes 1 , 3 and 4 established the formation of mononuclear compounds, containing one bidentate ligand unit per metal atom, to give square planar complexes. All the other spectroscopic characterization data and elemental analyses were consistent with the observed structures. All the palladium (II) complexes 1–4 gave active catalysts in the methoxycarbonylation of 1‐octenes. The catalysts demonstrated 100% chemoselectivities towards esters and favored the formation of linear isomers. Reaction conditions such as the type of phosphine derivative, acid promoter, solvent system, time, pressure and temperature have been investigated and shown to affect both the catalytic activity and regio‐selectivity of the catalysts. Solid‐angle modelling established the comparable steric contributions from the ligands, consistent with the similar regioselectivities of the resultant catalysts. 相似文献
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We reported here four structures of lanthanide–amino acid complexes obtained under near physiological pH conditions and their individual formula can be described as [Tb2(dl-Cys)4(H2O)8]Cl2 (1), [Eu4(μ3-OH)4(l-Asp)2(l-HAsp)3(H2O)7] Cl · 11.5H2O (2), [Eu8(l-HVal)16(H2O)32]Cl24 · 12.5H2O (3), and [Tb2(dl-HVal)4(H2O)8]Cl6 · 2H2O (4). These complexes showed diverse structures and have shown potential application in DNA detection. We studied the interactions of the complexes with five single-stranded DNA and found different fluorescence enhancement, binding affinity and binding stoichiometry when the complexes are bound to DNA. 相似文献
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Jose' VicenteMaría Dolores Bermúdez Francisco J. Carrin Gins Martínez-Nicolas 《Journal of organometallic chemistry》1994,480(1-2):103-109
Liquid crystalline 4-XC6H4N=NC6H4X-4′ [X = C4H9 (1a), C1OH21 (1b), OC4H9 (1c), OC8H17(1d)] can be easily prepared in high yields from the corresponding anilines. In order to study the influence of metals on the thermal properties of these materials, we have obtained adducts [AuCl 3(4-C4H9OC6H4N=NC6H4OC4H9-4′)] (2) and [Ag(OC1O3)L2] [L = 4-XC6H4N=NC6H4X-4′; X = OC4H, (3a), OC8H17 (3b)]. The silver adducts show themotropic behaviour. Mercuriation of dialkylazobenzenes 1a-b takes place with [Hg(OAc)2] and LiCl to give [Hg(R)Cl] [R = C6H3(N=NC6H4X-4′)-2, X-5; X = C4H9 (bpap) (4a), C10H21 (dpap) (4b)] while dialkoxyazobenzenes 1c–d require [Hg (OOCCF3)2] to obtain [Hg(R)Cl] [R = C6H3(N---NC6H4X-4′)-2, X-5; X = OC4H9 (bxpap) (4c), OC 8H17 (4d)]. 4a-c react with NaI to give [HgR2] [R= bpap (5a), dpap (5b), bxpap (5c), oxpap (5d)l. Both chloroaryl-, 4a and 4c, and diaryl-mercurials, 5a and 5c, act readily as transmetailating agents towards [Me4N] [AuCl4] in the presence of [Me4N]Cl to give [Au(η2-R)Cl2] [R = bpap (6a), bxpap (6b)]. After reaction of [AuCl 3(tht)] (tht = tetrahydrothiophene) with [Me4N]Cl and 4b (1:2:1), [Me4N][Au(dpap)Cl3] (7) can be isolated. C---H activati bxpap (8b)]. None of the complexes 4–8 shows mesomorphic behaviour. 相似文献
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The thermal behaviour of [Co(en)n(phen)m]Cl3 complexes has been studied using thermogravimetry (TG), differential thermogravimetry (DTG) and differential thermal analysis (DTA) in air, nitrogen and oxygen atmospheres. The effect of the stoichiometry of the complexes and that of the gas atmosphere in the furnace chamber on the thermal decomposition reaction is evidenced and discussed. The following thermal stability order has been found [Co(en)3]Cl3 [Co(en)2(phen)]Cl3 > [Co(en)(phen)2]Cl3 [Co(phen)3]Cl3 相似文献
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Reaction of potassium 3{5}-(3′,4′-dimethoxyphenyl)pyrazolide with 2-bromopyridine in diglyme at 130°C for 3 days followed by an aqueous quench, affords 1-{pyrid-2-yl}-3-{3′,4′-dimethoxyphenyl}pyrazole (L2) in 69% yield after recrystallization from hot hexanes. Complexation of [Cu(NCMe)4]BF4 by 2 molar equivalents of 1-{pyrid-2-yl}-3-{2′,5′-dimethoxyphenyl}pyrazole (L1) or L2 in MeCN at room temperature, followed by concentration and crystallisation with Et2O, gives [Cu(L)2]BF4 L = L1, L2) in good yields. Treatment of AgBF4 with L1 or L2 in MeNO2 similarly gives [Ag(L)2]BF4 L = L1, L2); reaction of AfBF4 with L2 in MeCN gives a product of stoichiometry [Ag(L2)(NCMe)]BF4. The 1H NMR spectra of the [M(L)2]BF4 complexes show peaks arising from a single coordinated environment. The single crystal X-ray structure of [Cu(L1)2]BF4 shows a tetrahedral complex cation with Cu---N = 2.011(8), 2.036(8), 2.039(8), 2.110(8) Å. The CuI centre is close to tetrahedral, the dihedral angle between the least-squares planes formed by the Cu atom and the N donor atoms of the two ligands being 88.3(3)°. Complexation of hydrated Cu(BF4)2 by L2 in MeCN at room temperature yields [Cu(L2)2](BF4)2. The cyclic voltammograms of the three AgI complexes in MeCN/0.1 M Bu4n NPF6 are suggestive of extensive ligand dissociation in this solvent. 相似文献
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光催化具有无污染、安全高效等优点,已成为环保领域的研究热点。 本文选择2,4-二(3,5-二甲基吡唑)-6-二乙基胺-1,3,5-三嗪(L1)和2, 6-二[3-(5-甲基吡唑基)]吡啶(L2)为配体、以RuCl3为金属源,合成了3种配合物[Ru(L1)Cl3](1)、[Ru(L2)2]·Cl3(2)和[Ru(L2)2]·(H2BTC)·(HBTC)·H2O(3),同时进行了IR、UV-Vis、TG及X射线衍射等表征,并对配合物在光催化降解罗丹明B方面进行了探讨,结果表明,配合物13均具有一定程度的光降解效果,降解效果分别为46.8%、44.7%和40.4%。 相同条件下,加入H2O2后的配合物13的降解效果比金属盐、配体及H2O2单独存在时的降解效果好。 相似文献
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Organosilicon backbone containing ligands 1,2-bis(dimethyl(2-pyridyl)silyl)ethane (L1) and 1,2-bis(dimethyl(3-quinolyl)silyl) ethane (L2) have been synthesized by treating 2-bromopyridine and 3-bromoquinoline with n-butyllithium and reacting the resulting lithiated products with 1,2-bis(chlorodimethylsilyl)ethane. The ligation of L1 and L2 with Pd(II), Ag(I) and Cu(II) has been investigated. The single crystal structures of L2, [Pd(L1)Cl2] (1), [Cu(L1)Br2] (3) and [PdCl2(L2)]2 (4) have been solved. All the three complexes are metallamacrocyclic in nature. The last one is 22-membered and the first example which has ligands containing organosilicon backbone. The geometry of Pd as well as Cu is very close to square planar. The Pd–N, Pd–Cl, Cu–N and Cu–Br bond distances (2.010(1)–2.027(3), 2.3063(10)–2.3114(4), 2.004(4)–2.018(5) and 2.4137(10)–2.4172(10) Å) are very close to sum of covalent radii, indicating strong ligation of L1 and L2 with the metal ions. 相似文献
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The nucleophile [ArTe−] generated in situ borohydride solution of Ar2Te2, reacts with 2-(chloromethyl) tetrahydrofuran and 2-(2-bromoethyl)-1,3-dioxolane resulting in L1 and L2, respectively. The complexes of palladium(II) and platinum(II) with L1/L2 having stoichiometries [MCl2·L2], [ML2](ClO4)2, [(DPPE)ML2](ClO)4)2, [(PPh3)2ML2](ClO4)2 and [(phen)ML2](ClO4)2 (where L = L1/L2 DPPE = Ph2PC H2CH2PPh2, PHEN = 1,10-phenanthroline and M = Pd/Pt) have been synthesized. IR, 1H, 125Te{1H} and 31P{1H} NMR and UV-vis spectral data of these species in conjunction with their molar conductance and molecular weight data have been used to authenticate the new species. In all complexes (1–20) the ligands L1 and L2 are coordinated through tellurium and in the complexes of formula [ML2](ClO4)2 (M = Pd, Pt) the ligand is bidentate with the oxygen atom used in complexation. In solution, complexes PtCl2L2 exist as a mixture of cis and trans isomers whereas only the trans isomer was observed for the palladium analogues. The [(phen)PdL2](ClO4)2(Q) quenches 1O2 readily. The plot of log [Q] vs time is linear. Mechanism compatible with the experimental observations is proposed. 相似文献
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Peter K. Byers Allan J. Canty Peter R. Traill Andrew A. Watson 《Journal of organometallic chemistry》1990,390(3):399-407
Oxidative addition of ethyl iodide to PdMe2(2,2′-bipyridyl) in (CD3)2CO gives the unstable “PdIMe2Et(bpy)”, which undergoes reductive elimination to form PdIR(bpy) (R = Me, Et), ethane, and propane. Ethene and palladium metal are also formed, and are attributed to decomposition of PdIEt(bpy) via β-elimination. Similar results are obtained with n-propyl iodide, although a palladium(IV) intermediate was not detected, but CH2=CHCH2X (X = Br, I) and PhCH=CHCH2Br give isolable complexes fac-PdXMe2(CH2CH=CHR)(L2) (R = H, Ph; L2 = bpy, phen). The propenyl complexes decompose at ambient temperature to form ethane, a trace of PdXMe(L2), and mixtures of [Pd(η3-C3H5)(L2)]X and [Pd(η3-C3H5)(L2)]-[Pd(η3-C3H5)X2]; for fac-PdBrMe2(CH2CH=CH2)(bpy) the major palladium(II) product is [Pd(η3-C3H5)(bpy)]Br. 相似文献
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TIAN Ruijing WANG Fuxiang DU Chunyu FENG Lijuan LIU Ying ZHANG Cailing PAN Qinhe 《高等学校化学研究》2014,30(6):889-893
Three novel compounds, [Co(en)3]2[Zr2(C2O4)7]·2H20(HNU-2, en=ethylenediamine), [Co(NH3)6]· [Ce(CzO4)3(H2O)]·H2O(HNU-3) and [Co(dien)2][Gd(C2On)3]·0.75H2O(HNU-4, dien=dethylenetriamine) were hydro- thermal synthesized based on the templates of [Co(en)3]C13, [C0(NH3)6]C13 and [Co(dien)2]C13, respectively. The Zr4+ Ce3+ and Gd3+ cations are all coordinated by four oxalates to form [M(C2O4)n(H2O)n]m (M=Zr, Ce or Gd; n=0 or 1; m=4 or 5), which are similar to [In(C2O4)4]5- in NKB-1, and can be regarded as 4-connected building units. The [M(C2O4)a(H2O)n]m units are connected via sharing the bis-bidentate bridging oxalate ligands to form binuclears in HNU-2 and 1D "zigzag" chains in HNU-3 and HNU-4. cular building units to design 3D open frameworks with It is suggested that these compounds could be used as mole- zeolite topologies. 相似文献
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Concepci n L pez Sonia P rez Xavier Solans Merc Font-Bardia 《Journal of organometallic chemistry》2002,650(1-2):258-267
The study of the reactivity of R---CH=N---(C6H4-2-SMe) with R=C6H5 or 2,4,6-Me3-C6H2 with palladium(II) salts is reported. These studies have allowed us to prepare and characterize the coordination complexes: cis-[Pd{R---CH=N---(C6H4-2-SMe)}Cl2] {R=C6H5 or 2,4,6-Me3-C6H2} and the cyclopalladated compounds [Pd{C6H4---CH=N---(C6H4-2-SMe)}Cl] and [Pd{(2-CH2-4,6-Me2-C6H2)---CH=N---(C6H4-2-SMe)}Cl]. The X-ray crystal structures of the latter complexes reveal that the thioimines act as a [Csp2, phenyl,N,S]− and as a [Csp3, N,S]− terdentate group, respectively. The study of the reactions of the cyclopalladated compounds with PPh3 is also reported. 相似文献
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A series of N-[4'-(dodecyloxy)resorcylidene]-4-(RO*)-anilines (HLn n = 1, R*O = (-)-cis-myrtanyl; n = 2, R*O = (-)-menthyl; n = 3, R*O = S-(-)-β-citronellyl; n = 4, R*O = R-(-)-2-octyl) has been synthesized and the mesomorphic properties investigated. These ligands are able to chelate a metal atom; accordingly three different series of palladium complexes, [(Ln)Pd(Ln)], [(Ln)Pd(Azoxy-6)] and [(L3)Pd(Ph-Pyn)] (where Azoxy-6 and PhPyn are cyclopalladated 4,4'-dihexyloxyazoxybenzene and 5-substituted-2-(4-substituted-phenyl)pyrimidine, respectively) have been prepared. The mesogenic HL3 and HL4 ligands exhibit a S*C phase, retained in [(L3)Pd(L3)], which changes to a cholesteric phase in [(L4)Pd(L4)] and becomes the more ordered S*H phase in the [(Ln)Pd(Azoxy-6)] (n = 3,4) derivatives. In contrast, in the [(L3)Pd(Ph-Pyn)] compounds the mesomorphic phase is a SA phase. 相似文献
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Two new half-sandwich zirconium(IV) complexes bearing salicylaldimine ligands of the type Cp*Zr[2-tBu-4-R-6-(CH=NiPr)C6H2O]C12[R=H(1), tBu(2)] were prepared by the reaction of Cp*ZrC13 with the corresponding lithium of salicylaldimine ligands 2-tBu-4-R-6-(CH=NiPr)C6H2OLi[R=H(LiLa), tBu(LiLb)]. Com- plexes 1 and 2 were characterized by 1H NMR, BC NMR spectroscopy and elemental analysis. When activated with AliBu3 and Ph3CB(C6F5)4, both complexes 1 and 2 exhibited reasonable catalytic activities for ethylene polymeriza- tion, producing polyethylenes with moderate molecular weight. Complexes 1 and 2 also exhibited reasonable catalyt- ic activities for ethylene copolymerization with 1-hexene, producing poly(ethylene-co-l-hexene)s with moderate molecular weight and reasonable 1-hexene content. 相似文献