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1.
The Raman and infrared spectra (4000200 cm?1) of (C4H4P)Mn(CO)3 and (C4D4P)Mn(CO)3, and of [C4H2(CH3)2P]Mn(CO)3 and [C4D2(CH3)2P]Mn(CO)3 in the liquid and solid states (10–400 K) have been investigated. A complete vibrational assignment is proposed and valence force fields of the (C5H5) and (C4H4P) cycles are compared. From these results, it is clearly shown that the (C4H4P) rings are more electrophilic and weaker π-electron donors than (C5H5) rings, this is in agreement with their chemical behavior. 相似文献
2.
3.
The reaction of M3(CO)12 (M = Ru, Fe) with excess bi-2,7-cyclooctadienyl (C16H22) 1 gave a mononuclear complex M(CO)3(1,2,1′-2′-η4-C16H22), 2a (M = Ru) or 3a (M = Fe), in good yield. Treatment of 2a with Fe3(CO)12 or reaction of 3a with Ru3(CO)12 gave the heterobimetallic complex RuFe(CO)6(C10H22) consisting of a ruthenacyclopentadiene unit coordinated to an Fe(CO)3 fragment, as confirmed by 1H NMR and X-ray studies. The corresponding homobimetallic complex Ru2(CO)6(C16H22) was obtained from the 1:1 reaction of 2a with Ru3(CO)12, while the direct reaction of 1 with Ru3(CO)12 gave Ru2(CO)6(C16H20) preferentially with a loss of two hydrogen atoms. The pathway for formation of these bimetallic complexes was interpreted as a dehydrogenative metallacyclization followed by hydrogen transfer. 相似文献
4.
The crystal structures of the Rh[(EtO)2PS2]3 (I) and Co[(PhO)2PS2]3 (II) chelate compounds were determined from X-ray diffraction (XRD) data (CAD-4 diffractometer, MoK
β radiation, 1193 F
hkl
, R = 0.0516 for I and 513 F
hkl
, R = 0.0305 for II). Crystals I are monoclinic: a = 14.233(3) Å, b = 13.570(3) Å, c = 14.272(3) Å; β = 90.66(3)°, V = 2756.3(10) Å3, Z = 4, ρcalc = 1.587 g/cm3, space group C2/c. Crystals II are trigonal: a = 15.149(2) Å, c = 30.306(6) Å; V = 6023.2(16) Å3, Z = 6, ρcalc = 1.493 g/cm3, space group R3ˉ. Structures I and II consist of discrete mononuclear molecules. The coordination polyhedra of the M atoms (M = Rh, Co)
are distorted octahedra formed by six sulfur atoms of three cyclic bidentate (RO)2 PS2− ligands.
Original Russian Text Copyright ? 2008 by R. F. Klevtsova, L. A. Glinskaya, and S. V. Larionov
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 2, pp. 330–334, March–April, 2008. 相似文献
5.
The reactions of [RuHCl(CO)(PPh3)3] and [(C6H6)RuCl2]2 with 2-benzoylpyridine have been examined, and two novel ruthenium(II) complexes – [RuCl(CO)(PPh3)2(C5H4NCOO)] and [RuCl2(C12H9NO)2] – have been obtained. The compounds have been studied by IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis. 相似文献
6.
Abby R O'Connor Chip Nataro James A Golen Arnold L Rheingold 《Journal of organometallic chemistry》2004,689(14):2411-2414
A new chemical oxidant [N(4-C6H4Br)3][B(C6F5)4], was prepared and used to synthesize [Fe(C5H5)2][B(C6F5)4]. The crystal structure of [Fe(C5H5)2][B(C6F5)4] was determined. 相似文献
7.
R.M. Medina A. Alvarez-Valdés J.R. Masaguer 《Journal of organometallic chemistry》1985,294(2):209-212
The complexes [η5-CH3C5H4Cr(CO)3]2 have been prepared, and their reactions with trivalent phosphorus ligands L (L = Ph3P, (MeO)3P, (EtO)3P) shown to give [η5-CH3C5H4Cr(CO)2L]2 complexes. 相似文献
8.
D. P. Domonov S. I. Pechenyuk N. L. Mikhailova A. T. Belyaevskii 《Russian Journal of Inorganic Chemistry》2007,52(7):1027-1032
The thermolysis of the complexes [Co(NH3)6]2C2O4[Cu(C2O4)2]2 (I) and [Co(NH3)6]Cl[Cu(C7H4O3)2] (II) in air and hydrogen at 200, 350, and 500°C and the composition and properties of the thermolysis products are considered.
The oxidative thermolysis of the complexes yields mixtures of cobalt and copper oxides, including mixed ones. The reductive
thermolysis of the complexes yields a Co + Cu bimetallic powder in the case of compound I and a Co + Cu + C powder in the
case of compound II. The thermal behavior of the complexes is governed by the nature of the ligand coordinated to the copper
atom. The observed data are explicable in terms of the properties of this ligand. The chemistry of the oxidative and reductive
thermolysis is discussed.
Original Russian Text ? D.P. Domonov, S.I. Pechenyuk, N.L. Mikhailova, A.T. Belyaevskii, 2007, published in Zhurnal Neorganicheskoi
Khimii, 2007, Vol. 52, No. 7, pp. 1104–1110. 相似文献
9.
The title compound (1) was prepared by the reaction of 3,5-bis(CF3)C6H3P(i-C3H7)2 (L1) and Co2(CO)8. Its solubility in supercritical carbon dioxide was measured at varying temperatures and pressures using a modified analytical extraction device. Solubility data were determined in the temperature and pressure ranges between 40 and 70 °C and between 100 and 300 bar, respectively. The solubility of 1 is lower compared to (p-CF3C6H4)3P, but much higher than for transition metal complexes bearing phosphines without fluorinated substituents. 相似文献
10.
The rates of the thermal reaction of the nickel(0) complex Ni[P(C2H5)3]4 with the alkyl halides CH3Br, CH3I in toluene have been compared with those of the reactions of the nickel(I) complexes Ni(X)[P(C2H5)3]3 (X Br,I). The organic products from CH3X are methane and ethane, and those from C2H5I are ethane and ethylene. The reactivity of the nickel(I) complexes is 10–20 times less than that of the nickel(0) complex. The result suggest that the first step of the reaction of nickel(0) with CH3I is the expected oxidative addition of the halide to the metal substrate. The intermediate thus formed decomposes to produce ethane (and small amounts of methane) without further reaction with the organic halide. This mechanism is supported by deuterium-labeling experiments. 相似文献
11.
The crystal and molecular structure of hexaphenylditin selenide (C6H5)3SnSeSn(G6H5)3 was determined by X-ray diffraction data and was refined to R 0.055. The compound is monoclinic, space group P21, with a 9.950(4), b 18.650(7), c 18.066(6) Å, β 106.81(4)°, Z 4. The two molecules in the asymmetric unit differ slightly in their conformations, both having approximate C2 symmetry. Bond lengths and angles are: SnSe 2.526 (2.521(3) ? 2.538(3)) Å; SnC 2.138 (2.107(16)?2.168(19)) Å; SnSeSn 103.4(1)°, 105.2(1)°. There are only slight angular distortions at the SnSeC3 tetrahedra (SeSnC angles: 104.3(5)?114.8(4)°). The bond data indicate essentially single bonds around the Sn atoms. 相似文献
12.
Diphenylcyclopropenethione reacts with Fe2(CO)9 in THF to give tetracarbonyl(diphenylcyclopropenethione)iron (C3Ph2S)Fe(CO)4. The crystal structure was determined by single crystal X-ray analysis. The compound crystallizes in the triclinic space group P with lattice constants a 1520.3(5), b 1026.1(3), c 933.5(2) pm; α 120.58(2), β 109.36(2), γ 111.72(2)°; Z 2. The molecule consists of an unchanged diphenylcyclopropenethione ligand coordinated via the sulphur atom to an Fe(CO)4 group in the axial position. The CS distance is 165.2(7) pm with an FeSC angle of 111.2(2)°. 相似文献
13.
Suhua Shi 《Journal of solid state chemistry》2004,177(11):4183-4187
A new vanadium(III) phosphite, (C4H8N2H4)0.5(C4H8N2H3)[V4(HPO3)7(H2O)3]1.5H2O, has been synthesized hydrothermally by using V2O5, H3PO3 as reactants, piperazine as the structure-directing agent. The as-synthesized product was characterized by powder X-ray diffraction, IR spectroscopy, inductively coupled plasma analysis, thermogravimetric analysis, and SQUID magnetometer. Single-crystal X-ray diffraction analysis shows that the title compound crystallized in the trigonal space group (No. 165) with the parameters: , , and Z=4. Its structure is built up by alternation of octahedral VO6 or VO5(H2O) and pseudo-pyramidal HPO3 units to form infinite 2D layers, and these layers are interconnected by sharing vertex-oxygen with octahedral VO6 units to generate a 3D open-framework structure with 12-membered ring channels in a and b directions, respectively, where there exist entrapped diprotonated and mono-protonated piperazine cations, and water molecules. Magnetic measurement indicates that paramagnetic behavior is observed down to 4 K. 相似文献
14.
Anne Astier Jean-Claude Daran Yves Jeannin Catherine Rigault 《Journal of organometallic chemistry》1983,241(1):53-68
Syntheses and single-crystal X-ray diffraction studies have been completed on two cycloruthenapentadienyl (CO)6Ru2L2 derivatives, with L = CH2OHC = CCH2OH and C2H5C=CCH2CH2OH respectively. Crystal data are as follows: for [(CO)3RuC4(CH2OH)4]Ru(CO)3·H2O, P21/c, a 13.72(1), b 9.501(4), c 14.86(1) Å, β 101.10(6)°, Rw = 0.052 for 1911 reflections; for [(CO)3RuC4(CH2CH2OH)2(C2H5)2]Ru(CO)3, P21/c, a 9.191(3), b 16.732(4), c 14.903(3) Å, β 113.61(4)°, Rw = 0.042 for 2865 reflections. Both compounds are built up from binuclear units, each unit being regarded as a Ru(CO)3 fragment π-bonded to a cycloruthenapentadienyl ring. The molecular parameters are compared with those of known cyclometallapentadienyl complexes of transition metals. The presence of a semi-bridging CO group is discussed. 相似文献
15.
en Two differnt crystal modifications of hexaphenyldigermanium sulfide (C6H5GeSGe(C6H5)3 (I and II were obtained by crystallization from hot benzene/methanol or form ethanol at 20°C. Single crystal X-ray structural analyses for both I (low temperature data at ?130°C) and II (at 20°C) (I, R = 0.046; II, R = 0.048) were performed. I is monoclinic, P21/c, with a = 11.020(3), b = 15.473(3), c 18.606(3) »,π = 106.92(2)°, Z = 4; II is orthorhombic, P212121, with a = 2.617(2), b = 17.345(3), c = 18.408(3) », Z = 4.The molecules have different conformeric structures with respect to a rotation of the (C6H6)3Ge groups around the Ge bonds with very similar bond lenghts and angles. Bond data for I(II) are: GeS 2.212(1) and 2.261(1) » (2.227(2) and 2.240(2) »); GeC 1.933(4) ? 1.971(4), mean 1.945(5) » (1.931(7)?1.954(7), mean 1.943(4) »); GeSGe 111.2(1)° (110.7(1)°). The Ge bond lenghts are comparable to those in thiogermanates and do not indicate significant π-bond contributions. 相似文献
16.
The complex dicarbonylbis(diphenylethylphosphine)platinum, Pt(CO)2[P(C6H5)2(C2H5)]2, crystallizes in either of the enantiomorphous space groups P3121 (No. 152) and P3221 (No. 154) with cell dimensions a = 10.64(1), c = 22.06(1) Å, U = 2163 Å3; pc = 1.564 g/cm3 for Z = 3, pm = 1.55(3) g/cm3. The intensities of 1177 independent reflections have been determined by counter methods with MoKα monochromatized radiation. The structure has been solved by the heavy atom method. The refinement, carried out by full-matrix least squares down to a final R factor of 0.042, has enabled the absolute configuration of the crystal sample (space group P3121) to be ascertained. The molecule is roughly tetrahedral, and has the metal atom lying on a two-fold axis of the cell. Bond parameters are: PtC = 1.92(2) Å, PtP = 2.360(4) Å, CPtC = 117(1)° and PPtP = 97.9(2)°. The PtC2 and PtP2 moieties make a dihedral angle of 86.0(3)°. The overall C2 symmetry of the molecule is probably only a statistically averaged situation, a disorder in the PtCO interactions being apparent from the orientations of the thermal ellipsoids of the C and O atoms. 相似文献
17.
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
18.
The 31P chemical shift of the (C6H5)3-nPXn ligands (X = Cl, Br, I; n = 0–3) is dominated by the electronegativity of the substituents. π bonding is only important for derivatives with three strongly electronegative substituents. The 31P chemical shift of the corresponding complexes (C6H5)3-nPXnCr(CO)5 is governed by the simultaneous effects of the electronegativity, steric hindrance and π bonding. The resonance parameter, δ', indicates an increasing (pring → dp)π and (dcr→ dp)π electron delocalization with halogen substitution. 相似文献
19.
(C6H(14)N2)[NH4(ClO4)3] is a newly developed porous hybrid inorganic-organic framework material with easy access and excellent detonation performances,however,its thermal properties is still unclear and severely hampered further applications.In this study,thermal behaviors and non-isothermal decomposition reaction kinetics of(C6H(14)N2)[NH4(ClO4)3] were investigated systematically by the combination of differential scanning calorimetry(DSC) and simultaneous thermal analysis methods.In-situ FTIR spectroscopy technology was applied for investigation of the structure changes of(C6H(14)N2) NH4(ClO4)3]and some selected referents for better understanding of interactions between different components during the heating process.Experiment results indicated that the novel molecular perovskite structure renders(C6H(14)N2)[NH4(ClO4)3] better thermal stability than most of currently used energetic materials.Underhigh temperature s,the stability of the cage skeleton constructed by NH4^+and ClO4^-ions determined the decomposition process rather than organic moiety confined in the skeleton.The simple synthetic method,good detonation performances and excellent thermal properties make(C6H(14)N2)[NH4(ClO4)3] an ideal candidate for the preparation of advanced explosives and propellants. 相似文献
20.
Jae J. Koh Wook-Hwan Lee Paul G. Williard William M. Risen 《Journal of organometallic chemistry》1985,284(3):409-419
Hydrocarbon solutions of PtPCy3(C2H4)2 (Cy = cyclohexyl) react rapidly with 8-quinolinecarboxaldehyde (1 equiv.) to yield tricyclohexylphosphine quinolinecarboxyl platinum hydride (1) and CH2CH2 (2 equiv.). Compound 1 reacts with CCl4 in hydrocarbons to give PtPCy3(NC9H6CO)Cl (2) and CHCl3. The compound PtPCy3(C2H4)2 also reacts with Ph2P(C6H4-o-CHO) and Ph2As(C6H4-o-CHO) to give PCy3PtPh2P(C6H4-o-CO)(H) (3) and PCy3PtPh2As(C6H4-o-CO)(H) (4), respectively. Compounds 1, 2, 3, and 4 were characterized by infrared and 1H NMR spectra, and the crystal structure of 3 was determined by X-ray diffraction. Crystals of 3 are monoclinic, with space group P21/n and Z = 4 with the unit cell dimensions a 9.7936(17), b 14.844(35), c 23.530(64) Å, β 91.817 (18)°, and V 3419.09(1.36) Å3. The structure is refined to final discrepancy factors of R = 0.055, and Rw = 0.064. The molecular structure of 3 is that ligating atoms are in a plane containing Pt. The position of the hydride was not located crystallographically, but the 1H NMR spectrum of 3, supports the presence of a terminal hydride that is cis to the carbonyl. The IR band of 3 at 2023 cm?1 which is assigned to ν(PtH), and the hydride cleavage reaction of 1 with CCl4, provide evidence for the PtH bond. 相似文献