共查询到20条相似文献,搜索用时 15 毫秒
1.
Corry Decker 《Journal of organometallic chemistry》2004,689(9):1691-1701
The reactions of [Fe3(CO)12] or [Ru3(CO)12] with RNC (R=Ph, C6H4OMe-p or CH2SO2C6H4Me-p) have been investigated using electrospray mass spectrometry. Species arising from substitution of up to six ligands were detected for [Fe3(CO)12], but the higher-substituted compounds were too unstable to be isolated. The crystal structure of [Fe3(CO)10(CNPh)2] was determined at 150 and 298 K to show that both isonitrile ligands were trans to each other on the same Fe atom. For [Ru3(CO)12] substitution of up to three COs was found, together with the formation of higher-nuclearity clusters. [Ru4(CO)11(CNPh)3] was structurally characterised and has a spiked-triangular Ru4 core with two of the CNPh ligands coordinated in an unusual μ3-η2 mode. 相似文献
2.
Mariappan Periasamy Chellappan RameshkumarAmere Mukkanti 《Journal of organometallic chemistry》2002,649(2):209-213
Alkyne-iron carbonyl complexes, prepared using Fe(CO)5-NaBH4-CH3COOH-amine-alkyne and Fe3(CO)12-amine-alkyne reagent systems, react with excess of amine at 25 °C to give cyclic imides in moderate to good yields. Further, unsaturated iron carbonyl species, prepared using the Fe(CO)5-pyridine-N-oxide system, react with alkynes to give the corresponding anhydrides. 相似文献
3.
Jean-Jacques Brunet Remi Chauvin Ousmane Diallo Bruno Donnadieu Joëlle Jaffart Denis Neibecker 《Journal of organometallic chemistry》1998,570(2):9166
KHFe(CO)4 reacts with tris(amino)phosphines by substitution at phosphorus leading to [bis(amino)phosphine]tetracarbonyliron complexes [(R1R2N)2PH]Fe(CO)4. The X-ray structure has been determined for R1=R2=Ph. Deprotonation of these complexes with KH affords stable potassium phosphidotetracarbonylferrates which can be alkylated or acylated at phosphorus. 相似文献
4.
5.
6.
The thermochemical behavior of the coordination compound [Fe(urea)6](NO3)3 was studied by simultaneous CG–TG–DTG–DTA and mass spectrometry methods non-isothermal conditions. The compound decomposes at 200 °C into a mixture of spinel-type oxides and hematite. The nature and particle size of the final decomposition products are strongly associated with the conditions during the thermal treatments, in particular the heating rate and the calcination temperature. A certain fraction of the products are formed as nanometric particles; they show superparamagnetic behavior at room temperature. The comparably low temperature of the calcination treatments of this compound is a promising perspective to attain small sized magnetic powders. 相似文献
7.
Eulalia Ramirez-Oliva Jorge Cervantes Francisco Cervantes-Lee Ramesh N. Kapoor Keith H. Pannell 《Journal of organometallic chemistry》1996,510(1-2):57-62
A transition metal-substituted silylacetylene [(η5-C5H5)Fe(CO)2SiMe2C]2, [FpMe2SiC]2 (I) was synthesized and characterized spectroscopically and structurally. I crystallized in the monoclinic space group P21/n, A = 13.011(3) Å B = 12.912(3) Å, C = 13.175(5) Å, β = 94.95(2). The acetylene linkage is reactive toward Co2(CO)8 to form I. Co2(CO)6 (II) which was also characterized spectroscopically and by single crystal X-ray diffraction. II crystallized in the orthorhombic space group Pbca, A = 17.64(2) Å, B = 14.225(10) Å, C = 24.49(2) Å. 相似文献
8.
Jouni Pursiainen Tapani A. Pakkanen Juhani Jääskeläinen 《Journal of organometallic chemistry》1985,290(1):85-98
A new ruthenium-rhodium mixed-metal cluster HRuRh3(CO)12 and its derivatives HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2 have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh3(CO)12: monoclinic, space group P21/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh3(CO)10(PPh3)2·C6H14: triclinic, space group P, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo3(CO)10(PPh3)2·CH2Cl2: triclinic, space group P, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)4? and (Ru(CO)3Cl2)2 tetrahydrofuran followed by acid treatment yields HRuRh3(CO)12 in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh3(CO)10(PPh3)2, which is closely related to HRuCo3(CO)10(PPh3)2 and HFeCo3(CO)10(PPh3)2. The phosphines are axially coordinated. 相似文献
9.
Wen-Yann Yeh Yen-Chung Liu Gene-Hsiang Lee 《Journal of organometallic chemistry》2004,689(6):1014-1018
[Cp4Fe4(CO)4] (1) reacts with p-BrC6H4Li and MeOH in sequence to afford the functionalized cluster [Cp3Fe4(CO)4(C5H4-p-C6H4Br)] (2), while the reaction of 2 with n-BuLi and MeOH produces [Cp2Fe4(CO)4(C5H4Bu)(C5H4-p-C6H4Br)] (3). The double cluster [Cp3Fe4(CO)4(C5H4)]2(p-C6H4) (4) has been prepared by treatment of [Cp4Fe4(CO)4] with p-C6H4Li2 and MeOH in sequence. The electrochemistry of 2 and 4, as well as the crystal structure of 4 have been investigated. 相似文献
10.
Pradeep Mathur Bala. Manimaran Md. Munkir Hossain Rupa Shanbag Jayshree Murthy Iyer S. Saranathan C. V. V. Satyanarayana Mohan M. Bhadbhade 《Journal of organometallic chemistry》1995,490(1-2):173-178
The methylene-bridged, mixed-chalogen compounds Fe2(CO)6(μ-SeCH2Te) (1) and Fe2(CO)6(μ-SCH2Te) (3) have been synthesised from the room temperature reaction of diazomethane with Fe2(CO)6(μ-SeTe) and Fe2(CO)6(μ-STe), respectively. Compounds 1 and 3 have been characterised by IR, 1H, 13C, 77Se and 125Te NMR spectroscopy. The structure of 1 has been elucidated by X-ray crystallography. The crystalsare monoclinic,space group P21/n, A = 6.695(2), B = 13.993(5), C = 14.007(4)Å, β = 103.03(2)°, V = 1278(7) Å3, Z = 4, Dc = 2.599 g cm−3 and R = 0.030 (Rw = 0.047). 相似文献
11.
Munetaka Akita Masako Terada Masako Tanaka Yoshihiko Morooka 《Journal of organometallic chemistry》1996,510(1-2):255-261
The structures of the versatile starting compounds for organoiron complexes, the cationic aqua complex [(η5-C5Me4Et)Fe(CO)2(OH2)]BF4 (1b) and the halide complexes (η5-C5Me5)Fe(CO)2-I (2a), (η5-C5Me4Et)Fe(CO)2-I (2b) and (η5-C5Me4Et)Fe(CO)2-Cl (3b), are characterized by X-ray crystallography. Complex 1b [Fe---O: 2.022(8) Å and 2.043(9) Å, two independent molecules] is the first structurally characterized example of organoiron aqua complexes. Details of the synthetic procedures for the above complexes and the labile cationic THF complexes [η5-C5R5)Fe(CO)2(THF)]BF4 (4) are disclosed, and the dissociation equilibrium of 4 is confirmed by means of variable temperature 1H-NMR as well as saturation transfer experiment. 相似文献
12.
The utility of photochemical methods for the directed synthesis of mixed-metal metal clusters has been explored. The 366 nm photolysis of a solution containing [PPN] [Co(CO)4] (PPN = (Ph3P)2N+) and Os3(CO)12 gives the new cluster [PPN][CoOs3(CO)13] in 33% yield. Irradiation of a mixture of Fe(CO)5 and H2Os3(CO)10 yields H2FeOs3(CO)13 in 95% yield, and photolysis of Ru3(CO)12 in the presence of H2Os3(CO)10 gives the new cluster H2RuOs3(CO)13. Details of these syntheses, their probable mechanisms, and the characterization of the new compounds are discussed. 相似文献
13.
Pradeep Mathur Radhe Shyam Ji Amrendra K. Singh 《Journal of organometallic chemistry》2010,695(17):1986-141
Photolysis of a hexane solution containing ironpentacarbonyl, 1-ferrocenyl-4-phenyl-1,3-butadiyne at low temperature yields six new products: [Fe(CO)2{η2:η2-PhCCCC(Fc)C(CCPh)C(Fc)Fe(CO)3}-μ-CO] (1), [Fe2(CO)6{μ-η1:η1:η2:η2-PhCCCC(Fc)-C(O)-C(Fc)CCCPh}] (2), [Fe2(CO)6{μ-η1:η1:η2:η2-FcCC(CC Ph)-C(O)-C(Fc)CCCPh}] (3), [Fe2(CO)6{μ-η1:η1:η2:η2-FcCCCC(Fc)-C(O)-C(Fc)CCCPh}] (4), [Fe(CO)3{μ-η2: η2-[FcCC(CCPh)C(CCPh)C(Fc)}CO] (5) and [Fe(CO)3{μ-η2: η2-[FcCC(CCPh)C(CCPh)C(Fc)}CO] (6) formed by coupling of acetylenic moieties with CO insertion on metal carbonyl support. In presence of CO, formation of another new product 2,5-bis(ferrocenyl)-3,6-bis(tetracarbonylphenylmaleoyliron)quinone (7) was observed which on further reaction with ferrocenylacetyene gave the quinone, 2,5-bis(ferrocenyl)-3,6-bis(ethynylphenyl)quinone (8). Structures of 1-5 and 8 were established crystallographically. 相似文献
14.
Fujico Iwasaki Martin J. Mays Paul R. Raithby Philip L. Taylor Peter J. Wheatley 《Journal of organometallic chemistry》1981,213(1):185-206
Twelve new trinuclear complexes containing terminal PH2Ph, edge-bridging PHPh and/or capping PPh ligands have been isolated from the reaction of M3(CO)12 (M = Ru or Os) with PH2Ph in refluxing solvents. HRu3(CO)10(PHPh) (IIIa) crystallises in the monoclinic space group P21/c with a = 8.761(3), b = 11.402(4), c = 22.041(7) Å,β = 98.89(2)°, and Z = 4. The structure was solved by a combination of direct methods and Fourier difference techniques, and refined by blocked-cascade least squares to R = 0.027 for 3676 unique observed intensities. The X-ray analysis shows that one edge of the Ru3 triangle is bridged by a hydride and the PHPh ligand, and that the phosphorus-bound hydrogen atom lies over the metal triangle and the phenyl group away from it. This provides an explanation for the ready formation of the capped species H2Ru3(CO)9(PPh) (Va) on pyrolysis of the edge-bridged complex as opposed to the previously reported conversion of HOs3(CO)10(NHPh) to an orthometallated derivative under similar conditions. An X-ray analysis of H2Ru3(CO)9-(PPh) (Va) confirms the capped geometry. the complex crystallises in the monoclinic space group P21/n with a = 9.323(4), b = 15.110(6), c = 45.267(15) Å,β = 91.84(3)°, and Z = 12. the structure was solved and refined using the same techniques as described previously. The final residual R is 0.061 for 4839 reflections. Some reactions of Va show that the phosphorous cap is difficult to displace and stabilises the molecule with respect to decomposition to non-cluster species. 相似文献
15.
Valerie F. Allen Ronald Mason Peter B. Hitchcock 《Journal of organometallic chemistry》1977,140(3):297-307
X-ray crystallographic analyses of H2Os3(CO)10, H(SC2H5)Os3(CO)10 and (OCH3)2Os3(CO)10 are reported. Although hydrogen atom positions have not been located, the essential isostructural nature of the three commplexes establishes the hydride ligands as bridging two metal atoms, separated by 2.670 Å, with a formal bond order of two; the bridging hydrido- and thiolato-ligands span an osmium---osmium bond of length 2.863 Å and formal bond order one; the two μ-methoxy ligands bridge two metal atoms separated by 3.078 Å which, by simple 18 electron rule counting, has a metal---metal bond order of zero. Some general comments are made on the structures of polynuclear transition metal carbonyls. 相似文献
16.
Richard D. Adams Burjor Captain Wei Fu Mark D. Smith Lei Zhu 《Journal of Cluster Science》2006,17(1):87-95
Two new compounds Pd2Os3(CO)12
, 13 and Pd3Os3(CO)12
, 14 have been obtained from the reaction of
with Os3(CO)12 at room temperature. The products were formed by the addition of two and three
groups to the Os–Os bonds of Os3(CO)12. Compounds 13 and 14 interconvert between themselves by intermolecular exchange of the
groups in solution. Compounds 13 and 14 have been characterized by single crystal X-ray diffraction analyses.Dedicated to Professor Brian F. G. Johnson on the occasion of his retirement – 2005. 相似文献
17.
Zhiyuan Huang Zaki K. Phelan Rachel L. Tritt Shelby D. Valent Daniel R. Griffith 《Tetrahedron letters》2018,59(37):3432-3434
A formal aza-Michael addition to tropone by way of tricarbonyl(tropone)iron and/or the tetrafluoroborate salt formed via protonation of the complex is reported. Tricarbonyl(tropone)iron smoothly undergoes the direct aza-Michael reaction with unhindered aliphatic amines under solvent free conditions in good yields. Meanwhile, the known cationic complex [(C7H7O)Fe(CO)3]BF4 (whose reaction with a small number of nucleophiles was previously reported) undergoes addition with an even broader array of amine nucleophiles. Finally, it was discovered that protecting the aza-Michael adduct as a carbamate was necessary for oxidative demetallation of the complex. 相似文献
18.
The structures of two carbonylphosphine complexes of chromium were determined by X-ray analysis. cis-Tricarbonyltriphosphinechromium(0), [(CO)3(PH3)3Cr], crystallizes in space group P21/m with a = 6.90± 0.01, b = 11.29±0.02, c = 6.41±0.01 Å, β = 93.80±0.08°, Z=2. The structure was solved by conventional methods and refined by least squares (R1 = 0.056). The idealized octahedral molecule shows approximate C3v, symmetry. The mean CrP-distance is 2.346±40.003 Å. Pentacarbonylphosphinechromium, [(CO)5(PH3)Cr], crystallizes in spacegroup Pnma with a = 12.23±0.02, b = 11.33±0.02, c = 6.61 ±0.01 Å, Z = 4. Cell dimensions and structural parameters are very similar to those of hexacarbonylchromium(0). In the crystal the PH3 group is disordered over three mutually cis-positions of the coordination octahedron. 相似文献
19.
Richard D. Adams István T. Horváth Brigitte E. Segmüller 《Journal of organometallic chemistry》1984,262(2):243-252
Thermal degradation of the cluster compound Os3(CO)8(PPh2H)(μ3-S)2 (I) at 125°C leads to decarbonylation and formation of the new ligand bridged hexanuclear cluster Os6(CO)14(μ-PPh2)2(μ3-S)3(μ4-S) (II) in 11% yield. Space Group: P, No. 2, a 10.427(5), b 13.552(3), c 17.919(3) Å, α 84.87(2), β 75.41(3), γ 78.43(3)°, V 2399(2) Å3Z = 2, ?calc 2.82 g cm?3. The structure was solved by the heavy atom method and refined (3223 reflections) to the final residuals R = 0.042 and Rw = 0.036. The molecule consists of two sulfido bridged open triosmium clusters which are linked by a bridging sulfido ligand and a bridging diphenylphosphino ligand. 相似文献
20.
The thermally stable solids Re2(CO)8[μ-InRe(CO)5]2 and Re4(CO)12[μ3-InRe(CO)5]4 could be obtained by treatment of In with Re2(CO)10 in a bomb tube. A mechanism of the formation of the latter cluster from the first one is proposed. Compared with Re2(CO)8[μ-InRe(CO)5]2, Re4(CO)12[μ3_InRe(CO)5]4 shows in polar solvents an unusual high stability, which can be explained by the higher coordination number of In with rhenium carbonyl ligands. Re4(CO)12-[μ3-InRe(CO)5]4 dissolves monomerically in acetone, where as Re2(CO)8[μ-InRe(CO)5]2 dissociates yielding Re(CO)5? anions. Single-crystal X-ray analyses of Re4(CO)12[μ3-InRe(CO)5]4 establish the metal skeleton. The central molecular fragment Re4(CO)12 contains a tetrahedral arrangement of four bonded Re atoms [ReRe 302.8 (5) pm]. The triangles of this fragment are capped with a μ3-InRe(CO)5 group each [InRe(terminal) 273.5 (7) pm; InRe (polyhedral) 281.8 (7) pm]. The bridging type of In atoms with the Re4 tetrahedron and the metal skeleton was realized for the first time. By treating Re4(CO)12[μ3-InRe(CO)5]4 with Br2 the existence of Re(CO)5 ligands could be proved by isolating BrRe(CO)5. 相似文献