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1.
Thermal production of hydrogen from butane-2,3-diol is achieved with rates of up to 125 catalyst turnovers per hour using the homogeneous rhodium catalysts, [Rh(bipy)2]Cl, [RhH(PiPr3)3] and [RhCl(PPh3)3]. (bipy = 2,2′-bipyridyl). 相似文献
2.
The coordination of 1,5-bis-(1′-phenyl-3′-methyl-5′-pyrazolone-4′)-1,5-pentanedione (BPMPPD) and 2,2′-bipyridine (bipy) with lanthanide ions in water-alcohol solution has been studied. Binuclear complexes of the types : Ln2(BPMPPD)3(bipy)2·nH2O (n = 2 for Y, n = 4 for Eu, Gd, Dy, Ho, Er, Tm and Yb); Ln2(BPMPPD)3bipy·nH2O (n = 10 for La, n = 3 for Pr, Nd, Sm and Tb) were formed. The compounds were characterized by elemental analysis, molar conductance, IR, UV, 1H NMR spectroscopy, thermogravimetric analysis and fluorescence spectra. 相似文献
3.
A rapid single-step method for the electrosynthesis of chloro and bromo complexes of palladium(II and IV), viz. M2[PdX4] and M2[PdX6], by the dissolution of a palladium anode in chloride or bromide containing media is described. Electrolysis of dilute HX solution in the presence of pyridine, 2,2′-bipyridyl or 1,10-phenanthroline gives rise to non-electrolytes, e.g. trans-[PdX2(py)2], [PdX2(bipy)] and [PdX2(phen)]. Anodic oxidation of palladium in HX medium in the presence of acetonitrile and benzonitrile also gives the non-electrolytes trans-[PdX2(CH3CH2NH2)2] and trans-[PdX2(C6H5CH2NH2)2], respectively. 相似文献
4.
Two mononuclear RuII complexes of polypyridyl ligands, cis-[Ru(bpy)2(4,4′-bpy)Cl](PF6)·H2O (1) and cis-[Ru(phen)2(CH3CN)2](PF6)2 (2) (bpy=2,2′-bipyridyl, 4,4′-bpy=4,4′-bipyridyl, and PHEN=1,10-phenanthroline), have been synthesized and characterized by elemental analyses, IR and UV–vis spectra. The crystal structures of both complexes have been determined by X-ray diffraction, indicating that each RuII center is hexa-coordinated (RuN5Cl for 1 and RuN6 for 2) and takes a distorted octahedral geometry. The favored feature of both complexes is that they are quite useful complex precursors for further constructing new functional architectures. 相似文献
5.
Kathryn M. Carlson-Day Thomas E. Concolino Judith L. Eglin
Chun Lin
Tong RenEdward J. Valente
Jeffrey D. Zubkowski
《Polyhedron》1996,15(24):4469-4478The singlet-triplet separations for the edge-sharing bioctahedral (ESBO) complex W2(μ-H)(μ-Cl)(Cl4(μ-dppm)2 · (THF)3 (II) has been studied by 31P NMR spectroscopy. The structural characterization of [W2(μ-H)2(μ-O2CC6H5)2Cl2(P(C6H5)3)2] (I) by single-crystal X-ray crystallography has allowed the comparison of the energy of the HOMOLUMO separation determined using the Fenske-Hall method for a series of ESBO complexes with two hydride bridging atoms, two chloride bridging atoms and the mixed case with a chloride and hydride bridging atom. The complex representing the mixed case, [W2(μ-H)(μ-Cl)Cl4(μ-dppm)2 · (THF)3] (II), has been synthesized and the value of −2J determined from variable-temperature 31P NMR spectroscopy. 相似文献
6.
The reaction of Cp(dppe)FeI with the ligands 2,2′- and 4,4′-dithiobispyridine (S2(Py)2) give the mononuclear or binuclear complexes of the type [Cp(dppe)Fe-S2(Py)2]PF6, [Cp(dppe)Fe---SPy]PF6 or [{Cp(dppe)Fe}2-μ-SPy](PF6)2 depending on the reaction condition. Reaction of Cp(dppe)FeI with dithiobispyridines in presence of TlPF6 as halide abstractor and using CH2Cl2 as a solvent gives the complexes [Cp(dppe)Fe-4,4′-S2(Py)2)2]PF6 (1) and [CpFe(dppe)-2,2′-S2(Py)2]PF6 (2) whereas the same reaction using CH3OH as a solvent and NH4PF6 as the halide abstractor leads to the formation of the FeIII–thiolate complex [Cp(dppe)Fe-2,2′-SPy]PF6 (3) and the mixed-valence complex [Cp(dppe)FeIII-μSPy-FeII(dppe)Cp](PF6)2 (4). Magnetic and ESR measurements are in agreement with one unpaired electron delocalized between them. Mössbauer data indicate clearly the presence of two different iron sites, each one of the N-bonded and S-bonded iron atoms, with intermediate oxidation state FeII---FeIII. An electron transfer intervalence absorption was observed for this complex at 780 nm (in CH2Cl2). By applying the Hush theory the intervalence parameters were obtained; =0.028, Hab=361 cm−1 which indicate Class II Robin–Day. Estimation of the rate electron transfer affords a value kth=6.5×106 s−1. Solvent effect on the intervalence transition follow the Hush prediction for high dielectric constants solvents which permit the evaluation of the outer and inner-sphere reorganizational parameters, which were analyzed and discussed. The electronic interaction parameters compare well with those found for electron transfer in metalloproteins. 相似文献
7.
Binuclear complexes [{Cu(NN)(PhNHpy)}2(μ-OH)2](PF6)2, where NN=2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen), have been synthesized and characterized by chemical analysis, conductance measurements and IR and electronic spectroscopy. The X-ray crystal structure of [{Cu(bipy)(PhNHpy)}2(μ-OH)2](PF6)2 shows a distorted square-planar pyramidal coordination for Cu(II), defined by two nitrogen atoms of bipy, two bridging oxygen atoms and the pyridinic nitrogen atom of the ligand. Magnetic susceptibility measurements (in the 4.8–290 K range) reveal coupling which is antiferromagnetic for the bipy complex (2J=−24.2 cm−1) and slightly ferromagnetic for the phen complex (2J=3.3 cm−1). The EPR spectra show the expected triplet signals. 相似文献
8.
Francisco Montilla Antonio Pastor Agustín Galindo 《Journal of organometallic chemistry》1999,590(2):1167-207
Treatment of the complex Mo(Nmes)(O)Cl2(dme) (mes=2,4,6-trimethylphenyl; dme=1,2-dimethoxyethane) with KTpMe2, NaCp and bipy gives the corresponding derivatives (TpMe2)Mo(Nmes)(O)Cl (1), CpMo(Nmes)(O)Cl (2) and Mo(Nmes)(O)Cl2(bipy) (3). Other oxo---imido compounds of composition Mo(Nmes)(O)(S2CNR2)2 (R2=C4H4 4, C5H10 5, iPr2 6) can be obtained by reacting Mo(Nmes)(O)Cl2(dme) with the appropriate dithiocarbamate salt. The NMR properties of 4–6 are consistent with the presence of two rapidly equilibrating dithiocarbamate ligands. The reaction of Mo(Nmes)(O)Cl2(dme) with different Grignard reagents, Mg(R)X, produces the trialkyl imido complexes Mo(Nmes)R3Cl (R=Me 7, CH2C(Me)2Ph 8, CH2SiMe3 9). 相似文献
9.
Alexander Constantin Filippou Ernst Otto Fischer
Helmut Guido Alt
《Journal of organometallic chemistry》1988,340(3):331-339trans-I(CO)2L2WCNEt2 complexes (L2 = 2,2′-bipyridyl (2,2′-bipy); 1,10-phenanthroline (ophen)) react with PR3 (R = Me, Et) and thus undergo substitution of the iodine ligand by the phosphine to yield the new, thermostable, cationic carbyne complexes, [(PR3)(CO)2L2WCNEt2]+ I−. The ionic character of the compounds has been established from electrical conductivity studies of their solutions. Spectroscopic investigations of the complexes, whose composition has been determined by elemental analysis, indicate that in this reaction the halogen ligand in the trans position has been displaced by the chelate ligand, while the phosphine ligand occupies a cis coordination site, relative to carbyne moiety. 相似文献
10.
《Journal of molecular catalysis. A, Chemical》2002,190(1-2):131-143
The reaction of norbornene (NBE) and norbornadiene (NBD) in the presence of seven-coordinate tungsten(II) and molybdenum(II) complexes of the [(CO)4M(μ-Cl)3M(SnCl3)(CO)3] and [MCl(M′Cl3)(CO)3(NCMe)2] (M=W, Mo; M′=Sn, Ge) types leads to ring-opening metathesis polymerization (ROMP) and to the formation of high molecular weight polymers. The geometric structure of these polymers was determined by means of 1H- and 13C-NMR spectroscopy. The monitoring of the reaction between cyclic olefins and the metal complex by means of 1H-NMR spectroscopy allowed us to observe the coordination of NBD to metal atoms in the initiation step of the polymerization process. Compounds of the [MCl(SnCl3)(CO)3(η4-NBD)] type prepared directly from [(CO)4M(μ-Cl)3M(SnCl3)(CO)3] or [MCl(M′Cl3)(CO)3(NCMe)2] (M=W, Mo) in the presence of an excess of NBD initiate the ROMP reaction immediately. The detection of the first-formed products in the reaction between the metal complex and cyclic olefins provides valuable information concerning the nature of the initiating species. 相似文献
11.
Ji-Hui Li Jin-Tao Wang Ping Hu Li-Yi Zhang Zhong-Ning Chen Zong-Wan Mao Liang-Nian Ji 《Polyhedron》2008,27(7):1898-1904
A series of Cu(II) complexes of disubstituted 2,2′-bipyridine bearing ammonium groups [Cu(L1−4)2Br]5+ (1–4, L1 = [5,5′-(Me2NHCH2)2-bpy]2+, L2 = [5,5′-(Me3NCH2)2-bpy]2+, L3 = [4,4′-(Me2NHCH2)2-bpy]2+, L4 = [4,4′-(Me3NCH2)2-bpy]2+ and bpy = 2,2′-bipyridyl) were synthesized, of which complexes 1 and 4 were structurally characterized. Both coordination configurations of Cu(II) ions can be described as distorted trigonal bipyramid. The interaction between all complexes and CT-DNA was evaluated by thermal-denaturation experiments and CD spectroscopy. Results show that the complexes interact with CT-DNA via outside electrostatic interactions and their binding ability follows the order: 1 > 2 > 3 > 4. In the absence of any reducing agents, the cleavage of plasmid pBR322 DNA by these complexes was investigated and the hydrolysis kinetics of DNA was studied in Tris buffer (pH 7.5) at 37 °C. Obtained pseudo-Michaelis–Menten kinetic parameters: 15.0, 13.6, 2.01 and 1.69 h−1 for 1, 2, 3 and 4, respectively, indicate that complexes 1 and 2 exhibit very high DNA cleavage activities. According to their crystal data, the high nuclease activity may be attributed to the strong interaction of the metal moiety and two ammonium groups with phosphate groups of DNA. 相似文献
12.
Xu-Fang Chen Li Liu Jian-Gong Ma Long Yi Peng Cheng Dai-Zheng Liao Shi-Ping Yan Zong-Hui Jiang 《Journal of Molecular Structure》2005,750(1-3):94-100
A series of chromium(III) complexes [Cr(bipy)(HC2O4)2]Cl·3H2O (1), [Cr(phen)(HC2O4)2]Cl·3H2O (2), [Cr(phen)2(C2O4)]ClO4 (3), [Cr2(bipy)4(C2O4)](SO4)·(bipy)0.5·H2O (4) and [Mn(phen)2(H2O)2]2[Cr(phen)(C2O4)2]3ClO4·14H2O (5) were synthesized (bipy=4,4′-bipyridine, phen=1,10-phenanthroline), while the crystal structures of 1 and 3–5 have been determined by X-ray analysis. 1 and 3 are mononuclear complexes, 4 contains binuclear chromium(III) ions and 5 is a 3D supromolecule formed by complicated hydrogen bonding. 1–3 are potential molecular bricks of chromium(III) building blocks for synthesis heterometallic complexes. When we use these molecular bricks as ligands to react with other metal salts, unexpected complexes 4 and 5 are isolated in water solution. The synthesis conditions and reaction results are also discussed. 相似文献
13.
Ekkehard Lindner Ulf Kehrer Manfred Steimann Markus Strbele 《Journal of organometallic chemistry》2001,630(2):3021-274
A series of novel heterobimetallic crown ether-like polyoxadiphosphaplatinaferrocenophanes cis-[1,1′-Fc(CH2O(CH2CH2O)nCH2CH2PPh2)2]PtCl2 (n=1–3) (4a–c) was synthesized in good yield by cyclization of the bis(phosphine) ligands 1,1′-Fc(CH2O(CH2CH2O)nCH2CH2PPh2)2 (n=1–3) (3a–c) and (PhCN)2PtCl2 under high dilution conditions in CH2Cl2. The bisphosphines 3a–c are obtained by reaction of the corresponding diols 1,1′-Fc(CH2O(CH2CH2O)nCH2CH2OH)2 (n=1–3) (1a–c) with: (i) CH3SO2Cl in CH2Cl2 and (ii) LiPPh2 in THF. Although the X-ray crystal structure of 4a shows that the cavity is large enough for the encapsulation of small metal cations, inclusion experiments of 4a–c with Group 1 cations, and Mg2+, or NH4+ in solution applying NMR titration and cyclovoltammetric methods reveal no evidence for the formation of host–guest complexes for 4a,b. In the case of 4c only the addition of Na+ or K+ leads to an insignificant effect. 相似文献
14.
15.
Judith Bravo Carlos Cativiela Rafael Navarro Esteban P. Urriolabeitia 《Journal of organometallic chemistry》2002,650(1-2):157-172
The chiral bis-imine (1R,2R)-C6H10-[E---N=CH---C6H3---3,4-(OMe)2]2 1 (LH) reacts with [Pd(OAc)2] (1:1 molar ratio; OAc=acetate) giving the orthometallated [Pd(OAc)(C6H2---4,5-(OMe)2---2-CH=N-(1R,2R)-C6H10---N=CH---C6H3-3′,4′-(OMe)2-κ-C,N,N)] 2 (abbreviated as [Pd(OAc)(L-κ-C,N,N)]), through C---H bond activation on only one of the aryl rings and N,N-coordination of the two iminic N atoms. 2 reacts with an excess of LiCl to give [Pd(Cl)(L-κ-C,N,N)] 3. The reaction of 3 with AgClO4 and neutral or anionic ligands L′ (1:1:1 molar ratio) affords [Pd(L-κ-C,N,N)(L′)](ClO4) (L′=PPh3 4a, NCMe 5, pyridine 6, p-nitroaniline 7) or [Pd(I)(L-κ-C,N,N)] 8. Complex 4a reacts with wet CDCl3 giving [Pd(C6H2---4,5-(OMe)2---2-CH=N-(1R,2R)---C6H10---NH2-κ-C,N,N)(PPh3)](ClO4) 4b as a result of the hydrolysis of the C=N bond not involved in the orthometallated ring. The molecular structure of 4b·CH2Cl2 has been determined by X-ray diffraction methods. Cleavage of the Pd---N bond trans to the Caryl atom can be accomplished by coordination of strongly chelating ligands, such as acetylacetonate (acac) or bis(diphenylphosphino)ethane (dppe), forming [Pd(acac-O,O′)(L-κ-C,N)] 9 and [Pd(L-κ-C,N)(dppe-P,P′)](ClO4) 12, while classical N,N′-chelating ligands such as 1,10-phenantroline (phen) or 2,2′-bipyridyl (bipy) behave as monodentate N-donor ligands yielding [Pd(L-κ-C,N,N)(κ1-N-phen)](ClO4) 10 and [Pd(L-κ-C,N,N)(κ1-N-bipy)](ClO4) 11. Treatment of 1 with PtCl2(DMSO)2 (1:1 molar ratio) in refluxing 2-methoxyethanol gives Cl2Pt[(NH2)2C6H10---N,N′] 13a and [Pt(Cl)(C6H2---4,5-(OMe)2---2-CH=N-(1R,2R)---C6H10---NH2-κ-C,N,N)] 13b, while [Pt(Cl)(L-κ-C,N,N)] 14 can be obtained by reaction of [Pt(μ-Cl)(η3-2-Me---C3H4)]2 with 1 in refluxing CHCl3. Complexes 2 and 3 catalyzed the arylation of methyl acrylate giving good yields of the corresponding methyl cinnamates and TON up to 847 000. Complex 3 also catalyzes the hydroarylation of 2-norbornene, but with lower yields and without enantioselectivity. 相似文献
16.
Hamid Reza Khavasi Anita Abedi Vahid Amani Behrouz Notash Nasser Safari 《Polyhedron》2008,27(7):1848-1854
The 2,2′-dimethyl-4,4′-bithiazole ligand (1), (dm4bt), and its Zn and Hg complexes have been prepared. A conformational property calculation at the DFT level for the ligand shows the anti conformation is energetically more stable by about 22.83 kJ/mol and the rotational barrier is about 32.01 kJ/mol for the anti → syn conversion, a phenomena happening during complex formation. The complexes [Zn(dm4bt)Cl2] (2) and [Hg(dm4bt)Cl2] (3) have spectral properties typical for d10 metal diimine systems. The structures of the ligand and the two complexes have been determined by the single crystal diffraction method. The X-ray structure determinations show that both complexes are four coordinated by two chloride atoms and one bidentate dm4bt. In the Hg complex one of the two chlorides is set at a semi-bridging position. 相似文献
17.
Treatment of mercury(II) halides and pseudohalides with complexes (NN)(L)M(CO)3 (L = py; NN = 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen); M = Mo, W) gives new tricarbonyl complexes. In all cases elimination of the pyridine ligand occurs and in some cases there is partial displacement of halogen from the mercuric halide. Treatment of bipy(py)W(CO)3 with mercuric chloride gives only an adduct. Conductivity, IR and electronic absorption are given, and possible formulations suggested. 相似文献
18.
Charles M. King R. Bruce King Nripendra K. Bhattacharyya M. Gary Newton 《Journal of organometallic chemistry》2000,600(1-2):63-70
Soluble homogeneous organophosphorus—nickel complexes have been used to detoxify polychlorinated biphenyls (PCBs) by catalyzed hydrodechlorination using NaBH2(OCH2CH2OCH3)2 as the hydrogen source. The reactions appear to proceed by NiL3 oxidative addition into C---Cl bonds followed by hydrogenolysis of the metal---carbon bond. In model experiments with decachlorobiphenyl, the cone angle of the organophosphorus ligand L was shown to be a key factor controlling the magnitude and position of chlorine displacement. Hence, ligands leading to para displacement (e.g. (o-MeC6H4O)3P), meta—para displacement (e.g. (EtO)3P and (PhO)3P), and ortho—meta—para displacement (e.g. Me3P and Et3P) were found. Significantly, the highly toxic, coplanar dioxin precursor 3,3′,4,4′-tetrachlorobiphenyl, a meta—para chlorine-substituted congener, was dechlorinated quantitatively with the Et3P catalyst system. Evidence for the presence of organonickel intermediates in the reaction mixtures was obtained by mass spectroscopic and X-ray diffraction studies. Of particular interest is the isolation of square planar complexes p-C6Cl5C6Cl4Ni(PEt3)2Cl from the reaction of decachlorobiphenyl with NaBH2(OCH2CH2OCH3)2—(Et3P)2NiCl2 as the catalyst precursor and m-C6Cl5C6Cl4Ni(PEt3)2Cl from decachlorobiphenyl—Ni(1,5-C8H12)2—PEt3 at room temperature. All are oxidative addition intermediates and precursors for decachlorobiphenyl hydrodechlorination. 相似文献
19.
Yong Li Jing Lu Jiqing Xu Xiaobing Cui Yinghua Sun Qingxin Yang Lingyun Pan 《Journal of Molecular Structure》2004,690(1-3):131-135
Nest-shaped cluster [MoOICu3S3(2,2′-bipy)2] (1) was synthesized by the treatment of (NH4)2MoS4, CuI, (n-Bu)4NI, and 2,2′-bipyridine (2,2′-bipy) through a solid-state reaction. It crystallizes in monoclinic space group P21/n, a=9.591(2) Å, b=14.820(3) Å, c=17.951(4) Å, β=91.98(2)°, V=2549.9(10) Å3, and Z=4. The nest-shaped cluster was obtained for the first time with a neutral skeleton containing 2,2′-bipy ligand. The non-linear optical (NLO) property of [MoOICu3S3(2,2′-bipy)2] in DMF solution was measured by using a Z-scan technique with 15 ns and 532 nm laser pulses. The cluster has large third-order NLO absorption and the third-order NLO refraction, its 2 and n2 values were calculated as 6.2×10−10 and −3.8×10−17 m2 W−1 in a 3.7×10−4 M DMF solution. 相似文献
20.
Automated sequential injection (SIA) method for chemiluminescence (CL) determination of nonsteroidal anti-inflammatory drug indomethacin (I) was devised. The CL radiation was emitted in the reaction of I (dissolved in aqueous 50% v/v ethanol) with intermediate reagent tris(2,2′-bipyridyl)ruthenium(III) (Ru(bipy)33+) in the presence of acetate. The Ru(bipy)33+ was generated on-line in the SIA system by the oxidation of 0.5 mM tris(2,2′-bipyridyl)ruthenium(II) (Ru(bipy)32+) with Ce(IV) ammonium sulphate in diluted sulphuric acid. The optimum sequence, concentrations, and aspirated volumes of reactant zones were: 15 mM Ce(IV) in 50 mM sulphuric acid 41 μL, 0.5 mM Ru(bipy)32+ 30 μL, 0.4 M Na acetate 16 μL and I sample 15 μL; the flow rates were 60 μL s−1 for the aspiration into the holding coil and 100 μL s−1 for detection. Calibration curve relating the intensity of CL (peak height of the transient CL signal) to concentration of I was curvilinear (second order polynomial) for 0.1–50 μM I (r = 0.9997; n = 9) with rectilinear section in the range 0.1–10 μM I (r = 0.9995; n = 5). The limit of detection (3σ) was 0.05 μM I. Repeatability of peak heights (R.S.D., n = 10) ranged between 2.4% (0.5 μM I) and 2.0% (7 μM I). Sample throughput was 180 h−1. The method was applied to determination of 1 to 5% of I in semisolid dosage forms (gels and ointments). The results compared well with those of UV spectrophotometric method. 相似文献