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1.
Compound [Fe2(μ-CO)2(CO)2(η5-C9H7)2] (1) reacts with aryllithium reagents, ArLi (Ar = C6H5, p-CH3C6H4, p-CF3C6H4) followed by alkylation with Et3OBF4 to give the diindenyl-coordinated diiron bridging alkoxycarbene complexes [Fe2{μ-C(OC2H5)Ar}(μ-CO)(CO)2(η5-C9H7)2] (2, Ar = C6H5; 3, Ar = p-CH3C6H4, 4, Ar = p-CF3C6H4). Complex 4 reacts with HBF4 · Et2O at low temperature to yield cationic bridging carbyne complex [Fe2(μ-CC6H4CF3-p)(μ-CO)(CO)2(η5-C9H7)2]BF4 (5). Cationic 5 reacts with NaBH4 in THF at low temperature to afford diiron bridging arylcarbene complex [Fe2{μ-C(H)C6H4CF3-p}(μ-CO)(CO)2(η5-C9H7)2] (6). The reaction of 5 with NaSC6H4CH3-p under the similar conditions gave the bridging arylthiocarbene complex [Fe2{μ-C(C6H4CF3-p)SC6H4CH3-p}(μ-CO)(CO)2(η5-C9H7)2] (7). Complex 5 can also react with carbonylmetal anionic compounds Na[M(CO)5(CN)] (M = Cr, Mo, W) to produce the diiron bridging aryl(penta-carbonylcyanometal)carbene complexes [Fe2{μ-C(C6H4CF3-p)NCM(CO)5}(μ-CO)(CO)2(η5-C9H7)2] (8, M = Cr; 9, M = Mo; 10, M = W). The structures of complexes 4, 6, 7, and 10 have been established by X-ray diffraction studies. 相似文献
2.
Reactions of the iridium(III) nitrosyl complex [Ir(NO)Cl2(PPh3)2] (1) with hydrosulfide and arenethiolate anions afforded the square-pyramidal iridium(III) complex [Ir(NO)(SH)2(PPh3)2] (2) with a bent nitrosyl ligand and a series of the square-planar iridium(I) complexes [Ir(NO)(SAr)2(PPh3)] (3a, Ar = C6H2Me3-2,4,6 (Mes); 3b, Ar = C6H3Me2-2,6 (Xy); 3c, Ar = C6H2Pri3-2,4,6) containing a linear nitrosyl ligand, respectively. Complex 1 also reacted with alkanethiolate anions or alkanethiols to give the thiolato-bridged diiridium complexes [Ir(NO)(mu-SPri)(SPri)(PPh3)]2 (4) and [Ir(NO)(mu-SBut)(PPh3)]2 (5). Complex 4 contains two square-pyramidal iridium(III) centers with a bent nitrosyl ligand, whereas 5 contains two tetrahedral iridium(0) centers with a linear nitrosyl ligand and has an Ir-Ir bond. Upon treatment with benzoyl chloride, 3a and 3b were converted into the (diaryl disulfide)- and thiolato-bridged dichlorodiiridium(III) complexes [[IrCl(mu-SC6HnMe4-nCH2)(PPh3)]2(mu-ArSSAr)] (6a, Ar = Mes, n = 2; 6b, Ar = Xy, n = 3) accompanied by a loss of the nitrosyl ligands and cleavage of a C-H bond in an ortho methyl group of the thiolato ligands. Similar treatment of 4 gave the dichlorodiiridium complex [Ir(NO)(PPh3)(mu-SPri)3IrCl2(PPh3)] (7), which has an octahedral dichloroiridium(III) center and a distorted trigonal-bipyramidal Ir(I) atom with a linear nitrosyl ligand. The detailed structures of 3a, 4, 5, 6a, and 7 have been determined by X-ray crystallography. 相似文献
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4.
Syntheses,structures, thermal stabilities and bacteriostatic activities of four lanthanide complexes
Four lanthanide complexes, [La2(2,4-DClBA)6(5,5′-DM-2,2′-bipy)2(H2O)2]·2C2H5OH (1) and [Ln(2,4-DClBA)3(5,5′-DM-2,2′-bipy)(C2H5OH)]2 (Ln = Pr(2), Sm(3), Gd(4); 2,4-DClBA = 2,4-dichlorobenzoate; 5,5′-DM-2,2′-bipy = 5,5′-dimethyl-2,2′-bipyridine), were synthesized and characterized via elemental analysis, infrared spectra and thermogravimetric analysis (TG). The crystal structures of 1 and 2–4 are different; Each La3+ is nine-coordinate adopting a distorted mono-capped square antiprism, while the Ln3+ ions of 2–4 are all eight-coordinate with a distorted square antiprismatic molecular geometry. There are subtle changes in the local coordination geometry of the lanthanide–5,5′-DM-2,2′-bipy complexes. Binuclear 1 complexes are stitched together via two kinds of hydrogen bonding interactions (OH?O and CH?O) to form 1-D chains along the y axis, while the units of 2–4 are stitched together via CH?O to form 1-D chains along the x axis. TG analysis revealed thermal decomposition processes and thermal stabilities of the complexes. The bacteriostatic activities of the complexes were evaluated against Candida albicans, Escherichia coli, and Staphylococcus aureus. 相似文献
5.
Nishiura M Baldamus J Shima T Mori K Hou Z 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(18):5033-5044
The acid-base reaction of [Ln(CH(2)SiMe(3))(3)(thf)(2)] with Cp'H gave the corresponding half-sandwich rare earth dialkyl complexes [(Cp')Ln(CH(2)SiMe(3))(2)(thf)] (1-Ln: Ln=Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Cp'=C(5)Me(4)SiMe(3)) in 62-90% isolated yields. X-ray crystallographic studies revealed that all of these complexes adopt a similar overall structure, in spite of large difference in metal-ion size. In most cases, the hydrogenolysis of the dialkyl complexes in toluene gave the tetranuclear octahydride complexes [{(Cp')Ln(μ-H)(2)}(4)(thf)(x)] (2-Ln: Ln=Sc, x=0; Y, x=1; Er, x=1; Tm, x=1; Gd, x=1; Dy, x=1; Ho, x=1) as the only isolable product. However, in the case of Lu, a trinuclear pentahydride [(Cp')(2)Lu(3)(μ-H)(5)(μ-CH(2)SiMe(2)C(5)Me(4))(thf)(2)] (3), in which the C-H activation of a methyl group of the Me(3)Si unit on a Cp' ligand took place, was obtained as a major product (66% yield), in addition to the tetranuclear octahydride [{(Cp')Lu(μ-H)(2)}(4)(thf)] (2-Lu, 34%). The use of hexane instead of toluene as a solvent for the hydrogenolysis of 1-Lu led to formation of 2-Lu as a major product (85%), while a similar reaction in THF yielded 3 predominantly (90%). The tetranuclear octahydride complexes of early (larger) lanthanide metals [{Cp'Ln(μ-H)(2)}(4)(thf)(2)] (2, Ln=La, Ce, Pr, Nd, Sm) were obtained in 38-57% isolated yields by hydrogenolysis of the bis(aminobenzyl) species [Cp'Ln(CH(2)C(6)H(4)NMe(2)-o)(2)], which were generated in-situ by reaction of [Ln(CH(2)C(6)H(4)NMe(2)-o)(3)] with one equivalent of Cp'H. X-ray crystallographic studies showed that the fine structures of these hydride clusters are dependent on the size of the metal ions. 相似文献
6.
《Journal of Coordination Chemistry》2012,65(1):56-66
[Cd2(C7H3NO5)2 · 4(H2O)] n · 3nH2O · 0.5n(CH3OH) (1) and [Cd3(C7H2NO5)2 · 10(H2O)] · 2H2O ·0.5CH3OH (2) were synthesized and characterized by X-ray single-crystal diffraction. The crystal structure of 1 reveals that both Cds are seven-coordinate with pentagonal bipyramid geometries. Coordination polyhedra are interlinked into a 1-D chain, further linked by hydrogen bonds into a 3-D network. Complex 2 is a discrete structure, then independent [Cd3(C7H2NO5)2 · 10(H2O)] are linked by hydrogen bonds into a 3-D network. The optical properties of 1 and 2 were investigated with fluorescent spectra; both exhibit strong green luminescence probably originating from π–π* transition of the ligand. 相似文献
7.
The syntheses and characterizations of a family of novel heteroleptic magnesium amide thiolates are presented. The compounds are synthesized by ligand redistribution chemistry involving reactions of equimolar amounts of magnesium amides and magnesium thiolates. Utilization of the smaller thiolates [Mg(SPh)2]n and [Mg(S-2,4,6-iPr3C6H2)2]n results in the isolation of dimeric species, [Mg(THF)(N(SiMe3)2)(mu-SR)]2 (R = Ph (1), 2,4,6-iPr3C6H2 (2)), with four-coordinate metal centers and bridging thiolate functions. The sterically more encumbered thiolate S-2,4,6-tBu3C6H2 induces the formation of the four-coordinate, monomeric species Mg(THF)2(N(SiMe3)2)(S-2,4,6-tBu3C6H2) (3)). Careful choice of reaction conditions allows the successful syntheses of pure heteroleptic compounds; however, it remains difficult to obtain the compounds in high yields, since a tendency toward product symmetrization and ligand redistribution under re-formation of the starting materials is prevalent. One of these symmetrized products is also included in this report: the dimeric, four-coordinate magnesium thiolate [Mg-(THF)(S-2,4,6-tBu3C6H2)(mu-S-2,4,6-tBu3C6H2)]2 (4), isolated as the product of the reaction between [Mg-(N(SiMe3)2)2]2 and Mg(THF)2(S-2,4,6-tBu3C6H2)2. All compounds were characterized by NMR and IR spectroscopy, elemental analyses, and X-ray crystallography. Crystal data obtained with Mo K alpha (lambda = 0.710 73 A) radiation are as follows. 1: C16H31MgNOSSi2, a = 11.2100(1) A, b = 17.4512(3) A, c = 11.2999(2) A, beta = 97.952(1) degrees, V = 2189.32(6) A3, Z = 4, monoclinic, space group P2(1)/n, R1 (all data) = 0.0934. 2: C25H49MgNOSSi2, a = 11.1691(1) A, b = 11.0578(1) A, c = 26.0671(4) A, beta = 99.906(1) degrees, V = 3171.44(6) A3, Z = 4, monoclinic, space group P2(1)/c, R1 (all data) = 0.0557. 3: C36H71MgNO3SSi2, a = 42.8293(16) A, b = 10.9737(5) A, c = 16.8305(7) A, beta = 98.755(3) degrees, V = 7818.1(6) A3, Z = 8, monoclinic, space group C2/c, R1 (all data) = 0.1331. 4: C80H132Mg2O2S4, a = 18.8806(2) A, b = 19.3850(2) A, c = 27.3012(4) A, beta = 97.250(1) degrees, V = 9912.4(2) A3, Z = 4, monoclinic, space group P2(1)/n, R1 (all data) = 0.1023. 相似文献
8.
Ana M Martins Rita Branquinho Jinlan Cui Alberto R Dias M.Teresa Duarte José Fernandes Sandra S Rodrigues 《Journal of organometallic chemistry》2004,689(14):2368-2376
[M(CpBz)(CO)3CH3] (M=Mo, 2a, W, 2b; CpBz=C5(CH2Ph)5) have been prepared and reacted with PCl5 and PhI · Cl2. Depending on the metal and on the chlorinating reagent used [Mo(CpBz)(η2-COCH3)Cl3], 3, [W(CpBz)Cl4], 4, [Mo(CpBz)(CO)3Cl], 5 and [Mo(CpBz)Cl4], 6 have been obtained. The molecular structures of all compounds are reported and two conformations have been characterised for the benzyl substituents. In complexes 2a, 2b and 5 one phenyl ring bends towards the metals while in 3 and 4 the five phenyls point opposite to the metals. 相似文献
9.
《Journal of Coordination Chemistry》2012,65(3):545-554
Two cadmium complexes, {[Cd2(2,5-tda)2(ip)4]·4H2O}n (1) and {[Cd2(4,4′-obb)2(ip)2·H2O]·H2O}n (2) (2,5-tda?=?thiophene-2,5-dicarboxylic acid, 4,4′-obb?=?4,4′-oxybisbenzoic acid, ip?=?1H-imidazo[4,5-f][1, 10]-phenanthroline), were synthesized and characterized by IR, elemental analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. X-ray analysis revealed that 1 is a dinuclear complex with the 2,5-tda anion connecting two Cd ions in a μ1-η1:η0/μ1-η1:η0 coordination mode. Each dinuclear complex is further connected with neighboring complexes via hydrogen-bonding interactions. Compound 2 displays a 2-D layer structure with opened windows occupied by crystallographic water molecules. The layers are further packed via hydrogen-bonding interactions. Luminescent properties for 1 and 2 are also investigated in the solid state at room temperature. 相似文献
10.
《Journal of Coordination Chemistry》2012,65(22):3895-3902
[Ni3(C13H9N2O)5(CH3OH)2] (1) and [Cd(C12H8N3)3] (2) were synthesized in methanol and characterized by elemental analyses, IR spectra, and X-ray diffraction. Complex 1 is trinuclear with three unsymmetric Ni(II)'s having different coordinated environments bridged by four oxygen atoms from five ligands. Intermolecular antiferromagnetic interactions were observed in 1. Complex 2 is mononuclear with Cd(II) six-coordinate by six nitrogen atoms from three bidentate HPBM anions. Complex 2 shows emission maxima in the blue region. 相似文献
11.
《Journal of Coordination Chemistry》2012,65(17):3007-3018
Syntheses, structures, and antimicrobial activities of cobalt(III) complexes with two tetradentate Schiff-base ligands, (BA)2en?=?bis(benzoylacetone)ethylenediimine dianion and (acac)2en?=?bis(acetylacetone)ethylenediimine dianion, and two axial pyridines (py) have been investigated. These complexes were characterized by FT-IR, 1H-NMR, UV-Vis spectroscopy, and elemental analysis. The crystal structures of the complexes were determined by X-ray crystallography. Single-crystal X-ray diffraction analyses revealed that both complexes have distorted octahedral environments, Schiff-base ligand coordinates cobalt in four equatorial positions, and the two axial positions are occupied by pyridines. The pyridines and Schiff-base ligands are involved in N–H···O hydrogen bonds with perchlorate. Biological activities of the ligands and metal complexes have been studied on Staphylococcus aureus, Escherichia coli, and Bacillus subtilis by the well diffusion method. The activity data show the metal complexes to be more potent than the parent ligand against two bacterial species. 相似文献
12.
《Journal of Coordination Chemistry》2012,65(1):18-27
Four new complexes, [M(C9H5N2O3)2(H2O)2]·CH3OH (M?=?Zn(II), Cd(II) and Mn(II)) (1–3) and [Cu(C9H5N2O3)2] (4), have been synthesized by reactions of 5-nitro-quinoline-8-yl acetate (NQA) and corresponding metal salts at room temperature and characterized by elemental analysis, IR, thermal gravimetric analysis (TGA), fluorescence measurement and single crystal X-ray diffraction. 1–3 are mononuclear, further extended to 2-D layers by hydrogen bonds. For 4, Cu2+ is coordinated by two N atoms and two O atoms from two NQ ligands. TGA indicates that 1–4 have good thermal stabilities. Furthermore, 1 and 2 show excellent luminescence in the solid state at room temperature. 相似文献
13.
《Journal of Coordination Chemistry》2012,65(12):997-1014
2?:?1 (L?:?M) Complexes of 2,6-bis(hydroxymethyl)pyridine (dhmp) with different Co(II) salts [CoCl2·6H2O, Co(SCN)2, Co(NO3)2·6H2O, CoSO4·7H2O and Co(OTos)2·6H2O] and Ni(II) salts [NiCl2·6H2O, Ni(NO3)2·6H2O, NiSO4·7H2O and Ni(OTos)2·6H2O] have been prepared (1–9) and studied by infrared spectroscopy and X-ray crystallography. Influences on the distortion of the coordination polyhedron, the arrangement of the donor atoms and the packing structure of the complexes were investigated in terms of the different kinds of anions and cations. In the metal chloride Complexes 1 and 2, water of hydration was found, while in Complex 3 the counterion (SCN–) acts as a ligand. The crystal structures of all complexes, except 3, show N2O4 hexacoordinated metal ions; in 3 the coordination environment is N4O2. Complex 1 is another exception in containing cobalt(III) instead of cobalt(II) as for the other complexes with cobalt salts. Logically, in Complex 1, one of the dhmp ligands is mono-deprotonated. In the neutral Complexes 2 and 4–9, the basal planes of the octahedra are made up of O donors and N atoms occupy the axial positions. In 1 as well as in 3, two N and two O atoms form the base, but in 1 O, and in 3 N atoms are on the axis of the coordination sphere. Moreover, the nickel Complexes 2, 5, 7 and 9 are more symmetrical in structure than the cobalt Complexes 1, 4, 6 and 8, in accordance with the Jahn–Teller effect. Packing structures of the complexes show specific interactions based on strong and weak H-bonds that involve the counterions, hydroxy groups and aromatic units, leading to extended network structures. 相似文献
14.
Long V. Dinh 《Journal of organometallic chemistry》2005,690(2):493-503
Reactions of diazocyclopentadiene and NBS at appropriate stoichiometries give 2,5-dibromodiazocyclopentadiene and 2,3,5-tribromodiazocyclopentadiene in 40% and 30% yields, respectively, after chromatography. These react with BrRe(CO)5 or BrMn(CO)5 (80 °C, CF3C6H5) to give (η5-1,2,3-C5H2Br3)M(CO)3 (3; M = a, Re; b, Mn) and (η5-C5HBr4)M(CO)3 (4a,b) in 75-85% yields. In the case of 4a, the intermediate η1-cyclopentadienyl complex (η1-C5HBr4)Re(CO)5 (4′a) can be isolated (44%). An isomer of 3b, (η5-1,2,4-C5H2Br3)Mn(CO)3, is accessed by desilylating previously reported (η5-1,2,4-C5(SiMe3)2Br3)Mn(CO)3 with CsF/MeOH (85%). The reaction of tetrabromodiazocyclopentadiene and BrRe(CO)5 at 80 °C in CF3C6H5 gives the η1-cyclopentadienyl complex (η1-C5Br5)Re(CO)5 (5′a, 74%) which cannot be induced to decarbonylate to (η5-C5Br5)Re(CO)3 (5a) under a variety of conditions. However, 5a can be isolated (45%) when a similar reaction is conducted at 120 °C. The IR properties of the preceding complexes are compared, and the crystal structures of 3a, 3b, 5a, and 5′a are determined and analyzed. 相似文献
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16.
Ziwei Gao Caiyun Zhang Mingyuan Dong Lingxiang Gao Guofang Zhang Zhaotie Liu Gaofeng Wang Denghui Wu 《应用有机金属化学》2006,20(2):117-124
Two 4‐coordinated titanocene complexes, [(η5‐C5H5)2Ti(O,O′)(5‐NO2‐OCC6H3)] (I) and [(η5‐C5H5)2Ti(2‐OH‐5‐NO2‐O2CC6H3)2] (II), have been synthesized by reaction of Cp2TiCl2 and 5‐nitrosalicylic acid in aqueous media. Single‐crystal X‐ray analyses of I and II display the mononuclear forms of TiIV, and geometries at titanium atoms are distorted tetrahedrons, while the coordination environment at TiIV in complex I is different from that in complex II. Crystallographic characterization revealed that each of the complexes exhibits a three‐dimensional framework constructed through weak interactions, which are H‐bonding, π–π stacking and C–H·π interactions, but they differ greatly when forming the three‐dimensional network structure in both complexes. The results show that the dramatic change of conditions has great effect on the molecular structure of 5‐nitrosalicylate titanocene, thereby significantly influencing the weak interactions and the specific framework structure. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
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18.
Hooshang Shahriari-Zavareh J. Fraser Stoddart M. Kevin Williams Billy L. Allwood David J. Williams 《Journal of inclusion phenomena and macrocyclic chemistry》1985,3(3):355-377
Whereas 1 1 crystalline complexes have been isolated between borane ammonia and methyl 4,6-O-benzylidene-2,3-dideoxy--d-galactopyranosido [2,3-b]-1,4,7,10,13,16-hexaoxacyclo-octadecane (1), methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-b] (methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-k]-1,4,7,10,13,16-hexaoxacyclo-octadecane (3), and (1R,2R,7R,24R)-3,5,8,11,14,17,20,23,26,28-decaoxatricyclo-[21.4.0.02,7]octacosane (4), the hosts, methyl, 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido[2,3-b] 1,4,7,10,13,16-hexaoxacyclo-octadecane (2) and 1,4 1,4 3,6 3,6-tetra-anhydro-2,2 5,5-bis-O-oxydiethylenedi-d-mannitol (5) have yielded 2 1 (guest:host) crystalline complexes with borane ammonia as guest. X-ray analyses of the supramolecular structures of BH3NH3 ·1, (BH3NH3)2 ·2, BH3NH3 ·3, BH3NH3 ·4, and (BH3NH3)2 ·5 have been carried out and BH3NH3 ·1, BH3NH3 ·2, and (BH3NH3)2 ·5 have been shown to reduce acetophenone with enantiomeric excesses of 5, 13, and 10% respectively.
Supplementary Data relating to this article (atomic coordinates of the hydrogen atoms and thermal parameters) are deposited with the British Library as Supplementary Publication No. SUP 82017 (74 pages).Dedicated to Professor H. M. Powell. 相似文献
19.
Guo-Ming Wang 《Journal of solid state chemistry》2006,179(5):1545-1553
Three new cobalt borate compounds, [Co(DIEN)2][B5O6(OH)4]2 (DIEN=diethylenetriamine) (1), [B5O7(OH)3Co(TREN)] (TREN=tris(2-aminoethyl)amine) (2), and [Co2(TETA)3][B5O6(OH)4]4 (TETA=triethylenetetramine) (3) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, elemental analysis and thermogravimetry. The structures exhibit interesting 3D supramolecular hydrogen-bonded architectures, involving the similar borate polyanion [B5O6+n(OH)4−n](n+1)−(n=0 for 1 and 3, and n=1 for 2) and the templating transition metal complexes which are generated in situ under mild solvothermal conditions. Crystal data: 1, monoclinic, space group C2/m (No. 12), , , , β=93.601(4)°, , Z=2; 2, monoclinic, P21/c (No. 14), , , , β=99.926(4)°, , Z=4; 3, triclinic, space group P-1 (No. 2), , , , α=77.009(5)°, β=80.095(2)°, γ=82.334(3)°, , Z=2. 相似文献
20.
稀土元素具有特殊的电子构型,使其在许多领域得到十分广泛的应用。稀土纳米化将有助于发现新性质、开拓新材料,因此,稀土纳米材料已经成为研究的热点。综述了各种形态稀土纳米材料的制备和性质、稀土纳米材料的复合与组装等方面的进展。 相似文献