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Conclusions The photochemical reactions of (CO)2(PPh3)MnC5H4Fe(CO)2C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)2C5H5 with PPh3 gave the products of replacing the CO on the Fe atom by PPh3: respectively (CO)2(PPh3)MnC5H4Fe (CO)(PPh3)C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)(PPh3)C5H5.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2813–2815, December, 1977.  相似文献   

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The beryllocenes [Be(C(5)Me(4)H)(2)] (1), [Be(C(5)Me(5))(2)] (2), and [Be(C(5)Me(5))(C(5)Me(4)H)] (3) have been prepared from BeCl(2) and the appropriate KCp' reagent in toluene/diethyl ether solvent mixtures. The synthesis of 1 is facile (20 degrees C, overnight), but generation of decamethylberyllocene 2 demands high temperatures (ca. 115 degrees C) and extended reaction times (3-4 days). The mixed-ring beryllocene 3 is obtained when the known [(eta(5)-C(5)Me(5))BeCl] is allowed to react with K[C(5)Me(4)H], once more under somewhat forcing conditions (115 degrees C, 36 h). The structures of the three metallocenes have been determined by low-temperature X-ray studies. Both 1 and 3 present eta5/eta1 geometries of the slip-sandwich type, whereas 2 exhibits an almost regular, ferrocene-like, sandwich structure. In the mixed-ring compound 3, C(5)Me(5) is centrally bound to beryllium and the eta(1)-C(5)Me(4)H ring bonds to the metal through the unique CH carbon atom. This is also the binding mode of the eta(1)-ring of 1. To analyze the nature of the bonding in these molecules, theoretical calculations at different levels of theory have been performed on compounds 2 and 3, and a comparison with the bonding in [Be(C(5)H(5))(2)] has been made. As for the latter molecule, energy differences between the eta5/eta5 and the eta5/eta1 structures of 2 are very small, being of the order of a few kcal mol(-1). Constrained space orbital variations (CSOV) calculations show that the covalent character in the bonding is larger for [Be(C(5)Me(5))(2)] than for [Be(C(5)H(5))(2)] due to larger charge delocalization and to increased polarizability of the C(5)Me(5) fragment.  相似文献   

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The iron complexes [(Et2Sb)4Fe4(CO)14] ( 1 ), [(nPr2Sb)4Fe3(CO)10] ( 2 ), [{(Me3SiCH2)2Sb}4Fe2(CO)6] ( 3 ), and [2‐(Me2NCH2)C6H4SbFe2(CO)8] ( 4 ) were prepared by reactions of distibanes with Fe2(CO)9. Compounds 1 – 4 were characterized by X‐ray diffraction, 1H NMR and IR spectroscopy as well as mass spectrometry; complex 1 was additionally characterized by density functional calculations.  相似文献   

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Trimethylamine‐tris(pentafluoroethyl)borane [(C2F5)3BNMe3] ( 1 ) reacts at 190 °C with water under displacement of the trimethylamine ligand to yield the hydroxy‐tris(pentafluoroethyl)borate [(C2F5)3BOH]? ( 2 ). In tributylamine 1 reacts with alkynes HC≡CR to form novel ethynyl‐tris(pentafluoroethyl)borate anions [(C2F5)3BC≡CR]? – R = C6H5 ( 3 ), C6H4CH3 ( 4 ), Si(CH(CH3)2)3 ( 5 ) – in moderate yields. Compound 3 adds water across the triple bond to form the novel anion [(C2F5)3BCH2(CO)C6H5]? ( 6 ). The structures of [(C2F5)3BNMe3], [NMe4][(C2F5)3BOH] and K[(C2F5)3BCH2(CO)C6H5] have been determined by x‐ray crystallography.  相似文献   

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The thermally unstable compound [Hg[P(C(6)F(5))(2)](2)] was obtained from the reaction of mercury cyanide and bis(pentafluorophenyl)phosphane in DMF solution and characterized by multinuclear NMR spectroscopy. The thermally stable trinuclear compounds [Hg[(mu-P(CF(3))(2))W(CO)(5)](2)] and [Hg[(mu-P(C(6)F(5))(2))W(CO)(5)](2)] are isolated and completely characterized. The higher order NMR spectra exhibiting multinuclear satellite systems have been sufficiently analyzed. [Hg[(mu-P(CF(3))(2))W(CO)(5)](2)].2DMF crystallizes in the monoclinic space group C2/c with a = 2366.2(3) pm, b = 1046.9(1) pm, c = 104.0(1) pm, and beta = 104.01(1) degrees. Structural, NMR spectroscopic, and vibrational data prove a weak coordination of the two DMF molecules. Structural, vibrational, and NMR spectroscopic evidence is given for a successive weakening of the pi back-bonding effect of the W-P bond in the order [W(CO)(5)PH(R(f))(2)], [Hg[(mu-P(R(f))(2))W(CO)(5)](2)], and [W[P(R(f))(2)](CO)(5)](-) with R(f) = C(6)F(5) and CF(3). The pi back-bonding effect of the W-C bonds increases vice versa.  相似文献   

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合成了稀土铁双核配合物:(C5H5Fe(CO)2)LnCl2·nTHF(Ln=Nd,Sm,Gd;n=1,2)和(C5H5Fe(CO)2)(C5H4(SiMe3))·LnCl·nTHF(Ln=Nd,Sm,Gd;n=0,1,2)。元素分析,热分析,红外光谱和质谱分析确认了这两种配合物。红外光谱数据表明铁与稀土原子是以羰基桥连接。晶体结构分析表明((C5H5Fe(CO)2)Na·4THF是(C5H5Fe(CO)2)LnCl2·nTHF合成的中间体。  相似文献   

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Four new thioantimonates(III) with compositions [(C3H10NO)(C3H10N)][Sb8S13] ( 1 ) (C3H9NO = 1‐amino‐3‐propanol, C3H9N = propylamine), [(C2H8NO)(C2H8N)(CH5N)][Sb8S13] ( 2 ) (C2H7NO = ethanolamine, C2H7N = ethylamine, CH5N = methylamine), [(C6H16N2)(C6H14N2)][Sb6S10] ( 3 ) (C6H14N2 = 1,2‐diaminocyclohexane) and [C8H22N2][Sb4S7] ( 4 ) (C8H20N2 = 1,8‐diaminooctane) were synthesized under solvothermal conditions. Compound 1 : triclinic space group P$\bar{1}$ , a = 6.9695(6) Å, b = 13.8095(12) Å, c = 18.0354(17) Å, α = 98.367(11), β = 96.097(11) and γ = 101.281(11)°; compound 2 : monoclinic space group P21/m, a = 7.1668(5), b = 25.8986(14), c = 16.0436(11) Å, β = 96.847(8)°; compound 3 : monoclinic space group P21/n, a = 11.6194(9), b = 10.2445(5) Å, c = 27.3590(18) Å, β = 91.909(6)°; compound 4 : triclinic space group P$\bar{1}$ , a = 7.0743(6), b = 12.0846(11), c = 13.9933(14) Å, α = 114.723(10), β = 97.595(11), γ = 93.272(11)°. The main structural feature of the two atoms thick layered [Sb8S13]2– anion in 1 are large nearly rectangular pores with dimensions 11.2 × 11.7 Å. The layers are stacked perpendicular to [100] to form tunnels being directed along [100]. In contrast to 1 the structure of 2 contains a [Sb8S13]2– chain anion with Sb12S12 pores measuring about 8.9 × 11.5 Å. Only if longer Sb–S distances are considered as bonding interactions a layered anion is formed. The chain anion [Sb6S10]2– in compound 3 is unique and is constructed by corner‐sharing SbS3 pyramids. Two symmetry‐related single chains consisting of alternating SbS3 units and Sb3S3 rings are bound to Sb4S4 rings in chair conformation. Finally, in the structure of 4 the SbS3 and SbS4 moieties are joined corner‐linked to form a chain of alternating SbS4 units and (SbS3)3 blocks. Neighboring chains are connected into sheets that contain relatively large Sb10S10 heterorings. The sheets are further connected by sulfur atoms generating four atoms thick double sheets.  相似文献   

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Reaction of C(NMe2)4 with Ni(CO)4 – Syntheses and Structures of [C(NMe2)3][(CO)3NiC(O)NMe2], [C(NMe2)3]2[Ni5(CO)12], and [C(NMe2)3]3[Ni6(CO)12][O2CNMe2] The reaction of C(NMe2)4 with Ni(CO)4 in THF produces the carbamoyl complex [C(NMe2)3][(CO)3NiC(O)NMe2] ( 1 ); side products are the purple cluster compound [C(NMe2)3]2[Ni5(CO)12] · THF ( 2 · THF) and the red cocristallization product [C(NMe2)3]3[Ni6(CO)12][O2CNMe2] ( 3 ). All compounds were studied by X‐ray diffraction analyses. The cations of 3 are all disordered but not those of 1 and 2 . The unit cell of 1 contains two crystallographically independent anions (I and II) which differ in the dihedral angle between the plane of the carbamoyl ligand and the plane defined by the atoms CCarbamoyl–Ni–CO amounting 0° in the anion I and 18° in the anion II.  相似文献   

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