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1.
《Polyhedron》1999,18(8-9):1153-1158
Some new calixarenes bearing boronic acid moieties, boronoalkylalkoxycalix[4]arenes, were synthesized by allylation, Claisen's rearrangement, alkylation, hydroboration and hydrolysis from 25,26,27,28-tetrahydroxycalix[4]arene and their structures were identified by elemental analysis, IR, 1H NMR, 13C NMR, 11B NMR, MS and UV spectra. The UV data showed that tetraalkoxycalix[4]arene tetraalkyltriboronic acid could coordinate significantly with carbohydrates. 相似文献
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A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O NS] ligand [2-Bu t 4-Me-6-((2-(SC 6 H 5)C 6 H 4 N = CHC 6 H 2 O)](La) and dianionic phenoxy-amine arylsulfide [O N S] ligand [2-Bu t 4-Me-6-((2-(SC 6 H 5)C 6 H 4 N-CH 2 C 6 H 2 O)] 2(Lb) have been synthesized and characterized.Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH 4 in cool diethyl ether.Half-sandwich Group IV metal complexes CpTi[O NS]Cl 2(1a),CpZr[O NS]Cl 2(1b),CpTi[O N S]Cl(2a),CpZr[O N S]Cl(2b) and Cp * Zr[O N S]Cl(2c) were synthesized by the reactions of La and Lb with CpTiCl 3,CpZrCl 3 and Cp * ZrCl 3,and characterized by IR,1 H-NMR,13 C-NMR and elemental analysis.In addition,an X-ray structure analysis was performed on ligand Lb.The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane(MAO) as co-catalyst up to 1.58 × 10 7 g-PE.mol-Zr 1.h 1.The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts. 相似文献
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Emmanuel Cadot Bernadette Salignac Sabine Halut Francis Scheresse 《Angewandte Chemie (International ed. in English)》1998,37(5):611-613
The pH-dependent self-condensation of the [Mo 2 S 2 O 2 ] 2+ complex fragment gives the wheellike Mo12 cluster depicted on the right (ball-and-stick model; large balls: S, medium balls: O, small balls: Mo). Applying this synthetic strategy to other starting materials could provide access to other polyoxothiometalates with well-defined cavities. 相似文献
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Tridentate dianionic arylsulfide free ligands [ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh] (Ar = Ph (3a); Ar = 2,4,6-trimethylphenyl (3b); Ar = 2,6-diisopropylphenyl (3c)) have been prepared by reduction of the corresponding imine compounds [ArN[double bond, length as m-dash]CHC(6)H(4)NHC(6)H(4)-2-SPh] (Ar = Ph (2a); Ar = 2,4,6-trimethylphenyl (2b); Ar = 2,6-diisopropylphenyl (2c)) with LiAlH(4) in high yields. Reactions of TiCl(4) with the tridentate dianionic arylsulfide free ligands (3a-3c) afford five-coordinate and four-coordinate titanium complexes [κS, κ(2)N-(ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh)TiCl(2)] (Ar = Ph (4a); Ar = 2,4,6-trimethylphenyl (4b)] and [κ(2)N-(ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh)TiCl(2)] (Ar = 2,6-diisopropylphenyl (4c)], respectively. The molecular structures of compounds 2b, 2c, 3b and 3c·HCl have been characterized by single crystal X-ray diffraction analyses. Complexes 2a-4c are characterized by IR,(1)H-NMR spectra, and elemental analysis. EXAFS spectroscopy performed on complexes 4b and 4c reveals the expected different coordination geometry due to steric hindrance effect. When activated by excess methylaluminoxane (MAO), 4a-4c can be used as catalysts for ethylene polymerization and exhibit moderate to good activities. 相似文献
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Keyes TE Gicquel E Guerin L Forster RJ Hultgren V Bond AM Wedd AG 《Inorganic chemistry》2003,42(24):7897-7905
The photophysical properties of acetonitrile solutions of [Ru(bpy)(3)](2+) and [S(2)Mo(18)O(62)](4-) are described. We discuss evidence for ion cluster formation in solution and the observation that despite the strong donor ability of the excited state of [Ru(bpy)(3)](2+) and its inherent photolability, adducts with [S(2)Mo(18)O(62)](4-) were photostable. Photophysical studies suggest that the quenching of the [Ru(bpy)(3)](2+) excited state by [S(2)Mo(18)O(62)](4-) occurs via a static mechanism and that binding is largely electrostatic in nature. Evidence is provided from difference spectroscopy and luminescence excitation spectroscopy for good electronic communication between [Ru(bpy)(3)](2+) and [S(2)Mo(18)O(62)](4-) with the presence of a novel, luminescent, inter-ion charge-transfer transition. The identity of the transition is confirmed by resonance Raman spectroscopy. 相似文献
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Dppf is one of the most useful and popular ligands in coordination chemistry. Its overwhelming success has overshadowed and arguably even delayed the development and use of closely related ferrocene-based ligands with two ligating N, O or S atoms. Recently, however, dynamic progress concerning such homo-donor ligands can be noted. This tutorial review describes the main results obtained over the past decade in order to introduce the reader to an exciting field which currently shows particularly rapid development. The material is organised in sections according to ligand type, followed by a section which summarises the applications reported so far. 相似文献
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Nickel(II) complexes of the monoanionic borato ligands [Ph2B(CH2SCH3)2] (abbreviated Ph2Bt), [Ph2B(CH2S(t)Bu)2] (Ph2Bt(tBu)), [Ph2B(1-pyrazolyl)(CH2SCH3)], and [Ph2B(1-pyrazolyl)(CH2S(t)Bu)] have been prepared and characterized. While [Ph2Bt] formed the square planar homoleptic complex, [Ph2Bt]2Ni, the larger [S2] ligand with tert-butyl substituents, [Ph2BttBu], yielded an unexpected organometallic derivative, [Ph2Bt(tBu)]Ni(eta2-CH2SBut), resulting from B-C bond rupture. The analogous thiametallacycle derived from the [S3] ligand, [PhB(CH2S(t)Bu)3] (PhTt(tBu)), has been structurally authenticated (Schebler, P. J.; Mandimutsira, B. S.; Riordan, C. G.; Liable-Sands, L.; Incarvito, C. D.; Rheingold, A. L. J. Am. Chem. Soc. 2001, 123, 331). The [SN] borato ligands formed exclusively the cis stereoisomers upon reaction with Ni(II) sources, [Ph2B(1-pyrazolyl)(CH2SR)]2Ni. Analysis of the Ni(II/I) reduction potentials by cyclic voltammetry revealed a approximately 600 mV anodic shift upon replacement of two thioether donors ([Ph2Bt]2Ni) with two pyrazolyl donors ([Ph2B(1-pyrazolyl)(CH2SCH3)]2Ni) consistent with the all thioether environment stabilizing the lower oxidation state of nickel. 相似文献
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Cafeo G Kohnke FH White AJ Garozzo D Messina A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(2):649-656
Calix[2]benzo[4]pyrrole m-6 and p-6, each containing two dipyrromethane moieties and two m-phenylene or p-phenylene units, respectively, were readily synthesised from pyrrole, 1,3- and 1,4-bis(1,1'-dimethylhydroxymethyl)benzene, (m-4 and p-4, respectively) and acetone. Macrocycles m-6 and p-6 were tested as receptors for a selection of anions, such as acetate, dihydrogenphosphate and fluoride. The X-ray structures of m-6 and p-6 and those of the complexes m-6F(-), m-6Cl(-) and m-6CH(3)COO(-) (with an nBu(4)N(+) counterion) were also determined. 相似文献
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Qiutian Liu Chunxi Zhang Changneng Chen Hongping Zhu Yuheng Deng Jinhua Cai 《中国科学B辑(英文版)》1997,40(6):616-623
In a reaction system consisting of FeCl2, tetrathiometallate and cycloalkylthiolate, two Fe4S4 cubanelike cluster compounds were obtained with the following crystallographic data: (PhCH2NMe3)2 [ Fe4S4 (SC5H9)4] (I), monoclinic space groupP21/c,a = 1.632 7(4),b=1.122 9(3),c = 2. 802 5(10) nm, β= 94.63(2)°, Z=4, andR= 0.074; (Et4N)2[F4S4(SC6HlI)4] (II), tetragod space group
,a = l.167 05(9),b = 1.167 06(2),c = 2.063 26(5) nm,Z = 2, Dobs = 1. 28 g/cm3, andR = 0. 078. The participation of cycloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure. Meanwhile, the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed.
Project supported by the National Natural Science Foundation of China and the Climbing Program Foundation of China. 相似文献
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Dienes Y Eggenstein M Neumann T Englert U Baumgartner T 《Dalton transactions (Cambridge, England : 2003)》2006,(11):1424-1433
A series of dithieno[3,2-b:2',3'-d]phosphole-based transition metal complexes, including Au, Fe, Pt, Rh and W as central metals have been synthesised and characterised. Structural investigations by X-ray single crystal crystallography supported the high degree of pi-conjugation in the dithienophosphole ligands. This essential requirement for potential applications in molecular electronics and optoelectronics provides small band gaps for the materials. Investigations toward the optoelectronic properties of the respective complexes by fluorescence spectroscopy indicated that systematic alterations of the electronic structure are connected to different variables such as transition metal employed, functionalisation of the dithienophosphole ligands as well as complex geometries. The investigated Pt-based complexes exhibit only poor photoluminescence whereas Rh-, W- and Fe-based species with silyl functionalised dithienophosphole ligands show appreciable photophysical properties. The Au complexes investigated exhibit strong photoluminescence properties with very intriguing features in terms of excitation and emission wavelengths, intensity as well as selectivity. 相似文献
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IR and Raman spectra of [Mo2O2S2(S2)2]2- were reported. The resonance Raman spectra and the depolarization ratios in CH3CN solution were measured. By using the data of crystal structure, the simplified normal coordinate calculation of the stretching vibrations for anion [Mo2O2S2(S2)2]2- was performed. The results obtained are useful to assign the vibrational bands of some Mo-Fe-S clusters. 相似文献
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Li‐Peng He Hong‐Liang Mu Bai‐Xiang Li Yue‐Sheng Li 《Journal of polymer science. Part A, Polymer chemistry》2010,48(2):311-319
Novel chromium catalysts based on bidentate phenoxy‐phosphinoyl (HO‐2R1‐4R2‐6(Ph2P?O)C6H2: R1 = R2 = H, 3a ; R1 = tBu, R2 = H, 3b ; R1 = R2 = tBu, 3c ; R1 = R2 = cumyl, 3d ; R1 = anthracenyl, R2 = H, 3e ) and thiophenol‐phosphine (HS‐2R1‐4R2‐6(Ph2P)C6H2: R1 = R2 = H, 4a ; R1 = SiMe3, R2 = H, 4b ) were prepared and characterized. Treatment with modified methyaluminoxane, these catalysts displayed moderate to high‐catalytic activities for ethylene polymerization. The activities of them were higher than those of the corresponding catalysts based on bidentate phenoxy‐phosphine ligands. Both the coordinated donors and the ortho‐substituent of the ligands played an important role in improving catalytic activity. The effects of reaction parameters, such as cocatalyst and Al/Cr molar ratio as well as reaction temperature, on ethylene polymerization behaviors were investigated in detail for two favorable catalytic systems, 3b /CrCl3(thf)3 and 4b /CrCl3(thf)3. Catalyst 4b /CrCl3(thf)3 displayed higher catalytic activity and better temperature tolerance for ethylene polymerization than 3b /CrCl3(thf)3. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 311–319, 2010 相似文献
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Summary. The reaction of NiCl2 · 6H2O, Na2MoO4 ċ 2H2O, and sulfur in a mixture of diethylenetriamine and 0.2 M ammonia solution (1:4) under solvothermal conditions leads to the formation of orange-red crystals of the oxothiomolybdate
Ni(dien)2[Mo2O2S6] (dien = diethylenetriamine) in nearly 100% yield. The structure consists of [Ni(dien)2]2+ cations and discrete dimeric [Mo2O2S6]2− anions. The compound crystallizes in the monoclinic space group P21/c (a = 8.726(2), b = 18.111(4), c = 14.419(3) ?, β = 101.686(3)°). Upon heating the compound decomposes in a single step starting at about 250°C. The final
decomposition product was identified by X-ray powder diffractometry as MoS2 and Ni3S2. Spectroscopic data as well as detailed synthetic procedures for Ni(dien)2[Mo2O2S6] are reported.
Received November 6, 2000. Accepted November 17, 2000 相似文献