Reaction of anhydrous YbC13 with 2 equiv, of sodium 2,4,6-tri-tert-butylphenoxide (ArONa, Ar=C6H2-t-Bu3-2,4,6) and 2 equiv, of potassium diphenyl amide in THF afforded the first bis(aryloxo) amido-lanthanide complex of (ArO)2Yb(NPh2)2K(THF)4 (1). In 1, the ytterbium and potassium were bridged via diphenyl amido ligands.The ytterbium metal center was coordinated to two oxygen atoms of aryloxide ligands and two nitrogen atoms of diphenyl amido ligands in a conventional distorted tetrahedral fashion, while the potassium interacted in η^2-fashion with two phenyl rings of the diphenyl amido ligands besides four THF molecules. 1 displayed moderate catalytic activities for the polymerization of methyl methacrylate and acrylonitrile. 相似文献
A Cu(Ⅰ) complex with mix ligands [Cu(HIm)2(PPh3)2](BF4) was synthesized and characterized by elemental analysis, IRspectroscopy and X-ray diffraction crystallography. The crystal belongs to monoclinic system and P21/c space group, with cell parameters, a=1.2836(3)nm, b=1.5089(3)nm, c=2.0661(4)nm, α=90°, β=101.464(4)°,γ=90°, V=3.9219(13)nm3, Z=4 and Dc=1.374mg·m-3. The Cu(Ⅰ) is coordinated by two Patoms from triphenylphosphine and two Natoms from imidazole to form the distorted tetrahedral geometry. 相似文献
Reaction of divalent (Ph2N)2Sm(THF)4 with 1 equiv, of azobenzene in THF and then crystallization of the product in DME-Et2O mixed solvent produced the complex of [(PhEN)(DME)Sm]E(μ-η^2:η^2-N2Ph2)2 (1) in 65.0% yield. In complex 1, azobenzene molecules were reduced to be dianionic Ph2N2^2- ligands, bridging two samarium ions in two η^2:η^2 fashions. One samarium ion was bonded to a DME molecule and a diphenyl amido ligand besides two Ph2N2^2- ligands. The unusual Ln-η^2-arene close interaction was found for the first time for diphenyl amido lanthanides. Complex 1 could catalyze the polymerization of methyl methacrylate and acrylonitrile 相似文献
1 INTRODUCTION During the past decade, a series of organic-inor- ganic hybrid compounds based on metal halide units have been prepared and studied[1]. The combination of organic and inorganic components at the mole- cular level affords us the opportunity to design new hybrid materials and modulate the properties of components[2]. As a result, some interesting proper- ties, such as non-linear optical[3], interesting magne- tic[4], efficient luminescence[2], ideal thermal and mechanical sta… 相似文献
Pentavalent bis(triorganosiloxy)triphenylantimony derivatives, Ph3Sb(OSiR3)2 (R = Me, Ph), were synthesized by reaction of triphenylantimony with trimethyl- or triphenylsilanol in the presence of tert-butylhydroperoxide by the mild reaction conditions (0-5 °C, 2 h). The reaction of triphenylantimony with diethanolamine in the presence of tert-butylhydroperoxide gave the cyclic compound Ph3Sb(OCH2CH2)2NH. The mixture of Ph3SbO and Ph3Sb(OCH2CH2NMe2)2 was obtained by the reaction of triphenylantimony with 2-(N,N-dimethylamino)ethanol in the presence of tert-butylhydroperoxide. 相似文献
An electron diffraction analysis of the molecular structures of 1,1,1,3,3,3-hexachloro-1,3-disilapropane and octachloro-1,3-disilapropane has been carried out. Deviations from the staggered conformation are indicated. The data may be approximated by models with C2 symmetry and a small tilt of the SiCl3 groups. The main bond lengths (rg) and bond angles obtained for (SiCl3)2 CH2 are: SiCl, 202.7(4); SiC, 186.6(6); CH, 109.8(24) pm, ClSiCl, 107.9(1); SiCSi, 118.3(7)°; and for (SiCl3)2CCl2: SiCl, 202.0(4); SiC, 190.2(9); CCl, 179.6(9) pm; ClSiCl, 109.5(1); SiCSi, 120.6(9); ClCCl, 110.9(16); SiCCl, 106.3(3)°. 相似文献
The [PdCl2(NH2(CH2)5CH3)2] complex was tested as catalyst for 1-heptyne semihydrogenation under mild conditions of temperature and pressure in homogeneous
and heterogeneous systems. Species were characterized by XPS and FTIR techniques.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
UV irradiation of [Et4N] [V(CO)6] in the presence of the tripod ligands (L) MeC(CH2PPh2)3 (cp3) and P(CH2CH2PPh2)3 (pp3) yields [Et4N] [V(CO)5L], cis-[Et4N] [V(CO)4L] and mer-[Et4N] [V(CO)3L] (where the meridional configuration for L = cp3 is uncertain). Except for [Et4N] [V(CO)5cp3], all these species were isolated. The complexes are characterized by their IR, 31P and 51V NMR spectra. 相似文献
The enthalpies of reactions 1 and 2 have been measured as ΔH(1) = ?142 ± 6 and ΔH(2) = ?112 ± 6 kJ mol?1 to determine whether thermochemical factors are a major influence in the formation of different reaction products (tcne = tetracyanoethylene). 相似文献
Irradiation of Cp∗Ru(CO)2CH3 (1) in C6D6 at room temperature yields Cp∗Ru(CO)2C6D5 and CH3D (where Cp∗ = n5-C5Me5). Cp∗Ru(CO)2CD3 (2) has also been prepared and similar irradiation in C6H6 yields Cp∗Ru(CO)2C6H5 (3) and CD3H. This latter reaction confirms that it is the methyl group bonded to ruthenium that is involved in the C-H activation process and not the methyl groups on the Cp∗ ligand system. The compound Cp∗Ru(CO)2C6H5 (3) has been prepared for the first time in good yield by the reaction of Cp∗Ru(CO)2Br with NaBPh4. X-ray crystal structures of both Cp∗Ru(CO)2CH3 (1) and Cp∗Ru(CO)2C6H5 (3) have been determined and the results are reported and discussed. 相似文献
1,2-Eliminations are a varied and extensive set of dissociations of ions in the gas phase. To understand better such dissociations,
elimination of CH2=CH2 and CH3CH3 from (CH3)2NH+CH2CH3 (1) and of CH4 from (CH3)2NH2+ are characterized by quantum chemical calculations. Stretching of the CN bond to ethyl is followed by shift of an H from
methyl to the bridging position in ethyl and then to N to reach (CH3)2NH2+ + CH2=CH2 from 1. CH3CH3 elimination by H-transfer to C2H5+ to form CH3NH+=CH2 + CH3CH3 also takes place. (CH3)2NH2+ eliminates methane by CN bond extension followed by β-H-transfer to give CH2=NH+ + CH4. Low-energy reactions resembling complex-mediated 1,2-eliminations occur and constitute a hitherto largely unrecognized type
of reaction. As in many complex-mediated reactions, these reactions transfer H between incipient fragments. They are distinguished
from complex-mediated processes by the fragments not being able to rotate freely relative to each other near the transition
state for reaction, as they do in complexes. Most 1,2-eliminations are ion-neutral complex-mediated, occur by the just described
lower energy reactions, have 1,1-like transition states, or utilize highly asynchronous 1,2 transition states. All of these
avoid synchronized 1,2-transition states that would violate conservation of orbital symmetry. 相似文献
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
The crystal and molecular structure of the complex Th[η5-(CH3)5C5]2[CH2-Si(CH3)3]2, which undergoes facile intramolecular cyclometalation to the thoracyclobutane Th[η5-(CH3)5C5]2(CH2)2Si(CH3)2, is reported. While the Th[η5-(CH3)5C5]2 ligation is unexceptional, the Th[CH2Si(CH3)3]2 fragment is highly unsymmetrical having Th-C (corresponding angle Th-C-Si) 2.51(1) Å (132.0(6)°) and 2.46(1) Å (148.0(7)°). This conformation, which appears to result from severe intramolecular non-bonded contacts, allows a methyl hydrogen atom of one CH2Si(CH3)3 ligand to approach within ca. 2.3 Å of the α-carbon atom of the other CH2Si(CH3)3 ligand. 相似文献
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
