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1.
Two new iron–selenolate complexes [Cp*Fe(μ-SeMe)3FeCp*] (Cp* = η5-C5Me5) (1) and [Cp*Fe(μ-SeMe)3FeCp*][FeCl3] (2) were prepared by the oxidative addition reaction of MeSeSeMe with [Cp*FeCl]2 in 25% and 20% yields, respectively. In refluxing toluene, the methyl groups in the selenolate ligands of complex 1 were removed, affording a cubane cluster [Cp*4Fe4Se4] (3) in 50% yield. Complex 1 was oxidized by HBF4 to give [Cp*Fe(μ-SeMe)3FeCp*][BF4] (4), and the reverse reduction reaction occurred in the presence of CoCp2. 相似文献
2.
Liladhar B. Kumbhare Amey P. Wadawale Vimal K. Jain Monika Sieger Wolfgang Kaim 《Inorganic chemistry communications》2010,13(4):475-478
Monoselenocarboxylate–bridged binuclear complexes of RhIII and IrIII, [(Cp1MCl)2(μ-SeCOAr)2] (1) (M = Rh or Ir; Cp1 = pentamethylcyclopentadienyl; Ar = Ph, C6H4Me–4), have been isolated either by the reaction between [Cp12M2(μ-Cl)2Cl2] with KSeCOAr in acetonitrile or by treatment of [Cp1MCl(solvent)2][PF6] with KSeCOAr in acetone. The novel binuclear complexes, [Cp1IrCl(μ-SeCOAr)(κ2-SeCOC6H3R–)IrCp1] (2) (R = H or Me-4) with ortho-metallation at one of the iridium centres have been isolated following the use of excess AgPF6. The single crystal structure of [Cp1IrCl(μ-SeCOC6H5)(κ2-SeCOC6H4–)IrCp1] (2a) exhibits two phenylcarboselenolate moieties situated in syn fashion with respect to the “Ir2Se2” plane, one of which leans towards the metal centre in order to undergo ortho-metallation after iridium–chlorine bond dissociation. 相似文献
3.
Carlos Alonso-Moreno José Sancho Fernando Carrillo-Hermosilla Antonio Otero Antonio Antiñolo Isabel López-Solera 《Inorganic chemistry communications》2009,12(2):184-186
Rac and meso ansa-zirconocenes [Zr{1-Me2Si(3-R-(η5-C9H5))(3-R′-(η5-C9H5))}Cl2] (R = Et, R′ = H; R = Pr, R′ = H; and R = Et, R′ = Pr) 4–9 have been prepared by the reaction of ZrCl4 with the corresponding dilithiated derivatives from the ligands {1-Me2Si(3-R-(η5-C9H5))(3-R′-(η5-C9H5))} (R = Et, R′ = H 1; R = Pr, R′ = H 2; and R = Et, R′ = Pr 3) in diethyl ether/toluene at ?78 °C. The molecular structure of rac [Zr{1-Me2Si(3-Et-(η5-C9H5))(3-Pr-(η5-C9H5))}Cl2] 8 has been determined by single crystal X-ray diffraction studies, which show a pseudotetrahedral environment formed by the two chlorine ligands and two η5-coordinated indenyl ligands. The activity in homogeneous and heterogeneous polymerization is compared and discussed. 相似文献
4.
Reaction of copper(II) nitrate trihydrate with N,N-dimethylethanolamine (dmea) and pivalic acid in methanol led to the hexanuclear copper(II) complex Cu6(η1:μ2-C4H10NO)4(η1:η1:μ2-C5H9O2)4(η1:μ1-C5H9O2)2(μ3-OH)2 (1). The crystal structure of 1 indicates that hexametallic centers are bridged by the μ3-alkoxo, dmea oxygens, and the μ2-dicarboxylato oxygen atoms of pivalate ions. Furthermore, in the asymmetric unit, three types of copper ions have been found labeled as Cu1, Cu2 and Cu3. The Cu2 takes a distorted octahedral shape, whereas Cu1 and Cu3 adopt square pyramidal geometries. The complex 1 shows strong antiferromagnetic interactions through the oxo groups within the dimeric units (J = − 82.6 to − 25.8 cm− 1) and weak antiferromagnetic couplings between the dimers (J = − 10.9 and 0.8 cm− 1). 相似文献
5.
《Inorganic chemistry communications》2008,11(10):1250-1252
A novel three-dimensional (3D) coordination polymer, [Cd(μ3-HIDC)(bbi)0.5]n (1) (H3IDC = 4,5-imidazoledicarboxylic acid, bbi = 1,1’-(1,4-butanediyl)bis(imidazole)), has been synthesized under microwave heating solvothermal conditions and characterized by elemental analysis, IR, TG, and single crystal X-ray diffraction. The crystal structure reveal that compound 1 consists of 2D brickwall-like networks of [Cd(μ3-HIDC)]n, which are further linked through μ2-bbi to generate a 3D structure. Compound 1 is stable up to 330 °C and displays strong blue fluorescent emission at room temperature. This work demonstrates that microwave-assisted solvothermal synthesis method is an efficient and fast way to prepare metal coordination polymers. 相似文献
6.
The in situ hydrothermal reaction of CuI, NaN3 and 4-(1H-imidazol-1-yl)benzonitrile leads to a new three-dimensional pillared-layer Cu(I)-MOF, [Cu2(μ3-I)(μ5-IPT)]n (1) (HIPT = 5-[4-(imidazol-1-yl)phenyl]tetrazolate). Interestingly, the structure of 1 exhibits an unprecedented binodal (4, 8)-connected three-dimensional self-penetrating framework first constructed from [Cu4I2]2 + cationic clusters as 8-connected nodes and in situ generated IPT ligands as 4-connected nodes. Moreover, 1 is strongly luminescent with green emission (λem = 545 nm) in the solid-state. 相似文献
7.
The reaction of Cu(II) salts with 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-t-butylphenol (Lt-Bu-OH) afforded two bridged-phenoxido/hydroxido complexes. The dinuclear bridged acetate species [Cu2(μ-Lt-Bu-O)(μ-CH3COO)](PF6)2 (1) and the 1D polymeric doubly-bridged-chlorido {[Cu2(μ-Lt-Bu-OH)(μ-Cl)2](ClO4)2·4H2O}n (2). The two complexes were structurally characterized. Both complexes revealed ferromagnetic interactions; moderate in complex 1 (J = + 30.8 cm− 1) and very weak (J = + 2.25 cm−1) in 2. 相似文献
8.
The new dinuclear rhodium complex [(Cp*RhCl)2(bpp)](PF6) ([1](PF6), Cp* = pentamethylcyclopentadienyl, bpp = 3,5-bis(2-pyridyl)pyrazolate) was synthesized by the reaction of [Cp*RhCl2]2 with 3,5-bis(2-pyridyl)pyrazole (bppH). [1](PF6) was characterized by 1H- and 13C{1H}-NMR spectroscopy and X-ray diffraction. The distance between the two Rh atoms in [1](PF6) is 4.746(3) Å. A cyclic voltammogram of [1](PF6) in acetonitrile shows three-step reduction peaks at Epc = − 1.44, − 1.68 and − 1.88 V (vs. Fc+/Fc), which are assigned to the reduction of the two Rh(III) centers and the bpp− ligand, respectively. [1](PF6) catalyzes the reduction reaction of NAD+ (nicotinamide adenine dinucleotide) using HCO2− as a reductant. 相似文献
9.
《Catalysis communications》2008,9(12):2025-2031
The asymmetric 3-oxa-pentamethylene bridged dinuclear titanocenium complex (CpTiCl2)2 (η5-C9H6(CH2CH2 OCH2CH2)-η5-C5H3 CH3) (1) has been prepared, characterized by 1H NMR spectroscopy and elemental analysis, and after activation with MAO tested as a homogenous catalyst for the polymerization of ethylene. The results show that the catalytic activity of 1 as well as the molecular weight of the produced polyethylene are higher than those using the alkylidene bridged asymmetric dinuclear metallocenes (CpTiCl2)2 (η5-C9H6(CH2) n-η5-C5H4), n = 3 (4), 4 (5). The molecular weight distribution of polyethylene produced with 1/MAO reaches 11.00 and the HT-GPC curve shows a bimodal distribution. The melting point of the polyethylene obtained by 1/MAO is higher than 135 °C and the 13C NMR spectrum of PE shows only one strong signal at 30 ppm for the methylene units indicating a highly linear and crystalline polymer. 相似文献
10.
The novel thiolate-bridged iron-ruthenium heteronuclear complex [(PPh3)(bdt)Ru(μ-η2:η4-bdt)FeCp*] (1, Cp* = η5-C5Me5, bdt = benzene-1,2-dithiolate) was prepared by one-electron reduction of complex [(PPh3)(bdt)Ru(μ-η2:η4-bdt)FeCp*][FeCl3] (1[FeCl3]) using CoCp2 as reducing agent. Meanwhile, complex 1 can also be one-electron oxidized by Fc·PF6 or HBF4 to regenerate the ionic complex 1[PF6] or 1[BF4]. Importantly, complex 1 shows good reactivity toward the catalytic N−N bond cleavage of hydrazine into ammonia. 相似文献
11.
A novel metal-organic framework, [Co6(μ3-OH)4(ndc)4(bip)2(H2O)2]n (1)[H2 ndc = 1,4-naphthalenedicarboxylic acid, bip = 1,5-bis(imidazole-1-yl)pentane], constructed from unique [Co6(μ3-OH)4]8 +n chains containing alternate [Co4(OH)2]6 + and [Co2(OH)2]2 + subunits, was reported, which has a new (3,3,8,12)-connected or 12-connented fcu/cubic network and shows weak antiferromagnetic interaction between the adjacent Co(II) ions mediated through the carboxylate and hydroxyl groups. 相似文献
12.
Xing-wu Tan Bai-mu Wang Ye Wang Shu-zhong Zhan 《Inorganic chemistry communications》2010,13(9):1061-1063
The Mannich reaction of 2-aminoethanol, 2-tert-butyl-4-methylphenol, and formaldehyde at the ratio sets of 1:2:2 provided a new ligand, N-(1-ethanol)-N,N-bis(3-tert-butyl-5-methyl-2-hydroxybenxyl)amine (H3L). In the presence of base, H3L reacted with FeCl3·6H2O to form a dinuclear Fe(III) complex [Fe2L2] 1. The value of μeff at room temperature (5.95 μB), is much less than the expected spin-only value (8.37 μB) of two high spin (hs) Fe3+ (S = 5/2) ions [μ = g[∑ ZS(S + 1)]1/2], indicating there were strong interactions between Fe3+ ions. The effective magnetic moment (μeff) decreased abruptly with cooling to a minimum value of 0.1 μB at 2 K. It was worth noting that Fe3+ ions of 1 exhibited thermally induced quartet ? doublet spin transitions, and these transitions were abrupt. The magnetic behaviors of 1 denoted the occurrence of intramolecular anti-ferromagnetic interactions. J (? 13.58 cm? 1) agrees with the result from Gorun–Lippard equation, ? J (cm? 1) = Aexp(BP(Å) = 12.9). 相似文献
13.
Three new coordination polymers, namely, {[Cu2(IPT)(SO4)(OH)(H2O)]·H2O}n (HIPT = 5-(4-(1H-imidazol-1-yl)phenyl)- 1H-tetrazolate, 1), {[Cd2(IPT)(NPA)(OH)]·H2O}n (H2NPA = 5-nitroisophthalic acid, 2), and {[Zn2(IPT)(IDC)(H2O)]·3H2O}n (H3IDC = 1H-imidazole-4,5-dicarboxylic acid, 3), were assembled from a bifunctional organic ligand containing both tetrazole and imidazole groups with/without the aid of carboxylate coligands. Compound 1 possesses 2D structure built by 1D [Cu2(IPT)(SO4)(OH)]n secondary building blocks and IPT− linkers. The 2D networks are linked into 3D supramolecular framework via water chains in helical conformation. Compound 2 displays 3D pillar-layer framework with 2D layers based on tetranuclear Cd(II) SBUs and NPA2 − pillars. Compound 3 exhibits a 3D framework constructed from the interconnection of 1D [Zn-IDC]n chains and binuclear Zn2(IPT)2 rings. The thermal stabilities of porous compound 3 and luminescent properties of compounds 2 and 3 have also been studied in detail. They exhibit intense solid-state fluorescent emissions at room temperature. 相似文献
14.
Feng Chen Fa-Kun Zheng Guang-Ning Liu A-Qing Wu Ming-Sheng Wang Sheng-Ping Guo Mei-Feng Wu Zhi-Fa Liu Guo-Cong Guo Jin-Shun Huang 《Inorganic chemistry communications》2010,13(2):278-281
Hydrothermal reaction of Cd(NO3)2, Co(NO3)2, Na(3-cba) and NaN3 yielded a 3D heterometallic coordination polymer, [Cd(μ5-3-tzba)(μ2-3-cba)(μ3-OH)Co(H2O)]n·2nH2O 1 (3-H2tzba = 3-(5H-tetrazol)benzoic acid and 3-Hcba = 3-cyanobenzoic acid), which was characterized by single-crystal X-ray diffraction. The in situ [2 + 3] cycloaddition reaction of nitrile and azide in presence of Cd(II) salt afforded tetrazolate-based 3-tzba2? ligand. In 1, metal-oxo chains [Cd(μ3-OH)Co]n are linked by 3-tzba2? in an unprecedented μ5-κN1:κN2:κN3:κN4:κO1,O2 coordination mode to form 2D layers, which are further pillared by 3-cba? to generate a 3D open framework encapsulating 1D chiral channels. Variable-temperature magnetic studies show that 1 exhibits antiferromagnetic interactions between Co(II) ions bridged by μ3-OH group. 相似文献
15.
A lanthanide coordination polymer based on H2sfdb ligand, namely [Tb4(sdbc)4(phen)2(μ3-OH)4]n ∙ 1.5nH2O (1) (H2sfdb = 4,4′-sulfonyldibenzoic acid, phen = 1,10-phenanthroline) has been hydrothermal synthesized and characterized. Compound 1 exhibits an unprecedented three-dimensional framework that comprised new cubane-like hydroxo clusters [Tb4(μ3-OH)4]8 + as the nodes and flexible (sfdb)2 − ligands as the linkers. In 1, (sfdb)2 − ligands display completely different four kinds of coordination modes. Interestingly, not only the carboxylate groups but also one oxygen atom of sulfonyl group of (sfdb)2 − ligand are coordinated with TbIII ions in 1, which is first found in the compounds based on H2sfdb ligand. The luminescence experiments show that TbIII compound exhibits the typical TbIII-centered luminescence. 相似文献
16.
《Inorganic chemistry communications》2007,10(2):191-194
We report on the first example of a light signal photodetecting device based on the new class of neutral bis(1,2-dithiolene) complexes [M(R-dmet)2], whose ligand is intermediate between those belonging to the classes dmit2− and R,R′-timdt2− (dmit2− = 2-thioxo-1,3-dithiole-4,5-dithiolato; R,R′-timdt2− = N,N′-disubstituted 2-thioxoimidazoline-4,5-dithiolato; R-dmet2− = N-substituted 2-thioxothiazoline-4,5-dithiolato). The device, hosting the active material [Ni(Et-dmet)2] (1) casted on a quartz substrate, acts as a photodetector responsive in a wide spectral range, reaching the appealing near-IR region, and features the highest efficiency values as compared to those based on the dithiolene complexes [Ni(Me,Non-timdt)2] (2) and [Pt(Et,Pent-timdt)2] (3). 相似文献
17.
Yunxia Hu Wenwei Zhang Xiaofei Zhang Zhilin Wang Yizhi Li Junfeng Bai 《Inorganic chemistry communications》2009,12(2):166-168
Two stable supramolecular microporous polymers with double-layer structures, [Co(AIP)(BPY)0.5 · H2O]n · 2nH2O (1) and [Ni(AIP)(BPY)0.5 · H2O]n · 2nH2O (2), were constructed from AIP (5-aminoisophthalate) and BPY (4,4′-bipyridine) under hydrothermal conditions. Both of them exhibit rarely reported (3,4)-connected (63)(658) topology and interesting water-induced reversible transformation properties that are confirmed by PXRD studies. 相似文献
18.
Under similar hydrothermal synthetic conditions using a novel flexible ligand 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetonitrile (PPAN), benzenedicarboxylate isomers (H2pa = phthalate, H2ip = isophthalate, and H2tp = terephthalate) and Cadmium(II) acetate, three novel mixed-ligand Cd(II) coordination polymers {[Cd2(PPAA)2(μ-pa)(H2O)]·2H2O}n (1), {[Cd4(PPAA)4 (μ4-ip)2]·2H2O}n (2) and {[Cd2(PPAA)2(μ-tp)]·2H2O}n (3) (PPAA− = 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl) acetate) have been isolated, in 1–3 PPAN, and are also hydrolyzed into a novel PPAA− ligand. Complex 1 is a 1D coordination polymer in which the tetra-nuclear [Cd4(PPAA)4]4 + structural units are extended by tri-dentate μ-pa2 − ligands. Complex 2 contains binuclear [Cd2(PPAA)2]4 + structural units, which are extended by four tetra-dentate μ4-ip2 − ligands to link eight neighboring binuclear [Cd2(PPAA)2]4 + units ultimately forming a 2D layered framework, while complex 3 contains 1D double chain containing [Cd(PPAA)]n cation structural units, which are further extended by tetradentate μ-tp2 − ligands to form a new 2D layered framework. All the complexes have been investigated by elemental analysis, FT-IR, thermal analysis and fluorescence characterization. The flexible coordination modes of PPAA− are also briefly analyzed. The flexible coordination modes of PPAA− and benzenedicarboxylate isomers also reveal great potential in the construction of these novel mixed-ligand luminescent frameworks with diverse structural motifs and unique functional properties. 相似文献
19.
The syntheses and properties of trans-[Ru(NH3)4(L)(NO)](BF4)3 (L = isonicotinic acid (inaH) (I) or ina-Tat48–60 (II)) are described. Tat48–60, a cell penetrating peptide fragment of the Tat regulatory protein of the HIV virus, was linked to the ruthenium nitrosyl through inaH. I and II release NO after reduction forming trans-[Ru(NH3)4(L)(H2O)]3 +. The IC50 values against B16-F10 melanoma cells of I and II (21 μmol L− 1 and 23 μmol L− 1, respectively) are close to that of the commercially available cisplatin (33 μmol L− 1) and smaller than similar complexes. The cytotoxicity is assigned to the NO released from I and II. 相似文献
20.
Anindita Mukherjee Rajesh Chakrabarty Goutam Kumar Patra 《Inorganic chemistry communications》2009,12(12):1227-1230
Two new coordination polymers [Cu(L1)2]n(ClO4)n·2nH2O (1), [Cu(L2)2]n(ClO4)n·2nH2O (2) of polydentate imine/pyridyl ligands, L1 and L2 with Cu(I) ion have been synthesized and characterized by single crystal X-ray diffraction studies, elemental analyses, IR′ UV–vis and NMR spectroscopy. They represent 3-dimensional, sixfold interpenetrating diamondoid network structures having large pores of dimension, 35 × 21 Å2 in 1 and 38 × 19 Å2 in 2, respectively. 相似文献