Single-electron oxidation of the known Cr(II) bis(amidinate) Cr[(Me3SiN)2CPh]2 (1) provides synthetic access to neutral Cr(III) complexes. The complexes Cr[(Me3SiN)2CPh]2X were prepared by reaction of 1 with AgO2CPh (X = O2CPh, 2), of 1 with iodine in THF (X = I/THF, 3), or of 1 with iodine in pentane, followed by addition of 2-adamantanone (X = I/2-adamantanone, 4). Treatment of 2 or 3 with C3H5MgCl resulted in the thermally stable allyl complex (X = η3-C3H5, 5). A preliminary kinetics study of the reaction of 1 with excess allyl benzoate and allyl acetate was performed. The molecular structures of 2, 3 and 5 were confirmed by single crystal X-ray diffraction. 相似文献
The binary complex salt [Co(N2C2H8)3][AuCl4]2Cl has been synthesized. Its crystal structure has been determined. Crystal data for C6H24N6Cl9AuCo: a = 20.8976(14) Å, b = 14.4773(9) Å, c = 7.9944(5) Å; β = 110.809(2)°; V = 2260.9(3) Å3, space group C2/c, Z = 4, dcalc = 2.798 g/cm3. The plane square environment of the gold atom of the complex anion is completed to a tetragonal pyramid by the chlorine atom of the neighboring complex anion (Au…Cl 3.538 Å). The structure is layered. Layers of complex cations and complex anions alternate along the X axis. 相似文献
The reactions of FeCl2.2H2O and 2,2,2-tris(1-pyrazolyl)ethanol HOCH2C(pz)3 (1) (pz = pyrazolyl) afford [Fe{HOCH2C(pz)3}2][FeCl4]Cl (2), [Fe{HOCH2C(pz)3}2]2[Fe2OCl6](Cl)2·4H2O (3·4H2O), [Fe{HOCH2C(pz)3}2][FeCl{HOCH2C(pz)3}(H2O)2]2(Cl)4 (4) or [Fe{HOCH2C(pz)3}2]Cl2 (5), depending on the experimental conditions. Compounds 1-5 were isolated as air-stable crystalline solids and fully characterized, including (1-4) by single-crystal X-ray diffraction analyses. The latter technique revealed strong intermolecular H-bonds involving the OH group of the scorpionate 2 and 3 giving rise to 1D chains which, in 3, are further expanded to a 2D network with intercalated infinite and almost plane chains of H-interacting water molecules. In 4, intermolecular π?π interactions involving the pyrazolyl rings are relevant.Complexes 2-5 display a high solubility in water (S25°Cca. 10-12 mg mL−1), a favourable feature towards their application as catalysts (or catalyst precursors) for the peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone, with aqueous H2O2/MeCN, at room temperature (TON values up to ca. 385). 相似文献
The B‐(triphenylgermyl)borazines 4 a and 4 b , the 1,2‐bis(dimethylamino)‐1,2‐bis(triphenylgermyl)‐diborane(4), 5 , and the (2,2,6,6‐tetramethylpiperidino)(triphenylgermyl)‐boranes 6 and 7 were prepared by allowing LiGePh3 to react with the corresponding B‐bromoborazines and aminochloroboranes, respectively. BH3 dissolved in thf readily adds to LiGePh3 generating Li(H3BGePh3), 8 a , in thf solution. Addition of N‐bases to the solution of 8 a produced (tmen · thf)Li(H3BGePh3), 8 b , and dimeric (py)2Li(H3BGePh3), 8 c . The borazine ring in 4 b is distorted into a boat shape. In 5 the NBGe planes are twisted against each other by 85°. Comparison with analogous (triphenylstannyl)boranes points to a more pronounced steric effect of the Ph3Ge group over the Ph3Sn group due to the shorter B–Ge bond. A fairly short B–Ge bond is found for the (triphenylgermyl)trihydroborates. The molecular structure of (Et2O)3LiGePh3 shows compressed C–Ge–C bond angles. Its molecular parameters fit well into the series LnLiEPh3 (E = Si, Sn, Pb). 相似文献
The condensation of D-mannose and D-galactose with aliphatic and aromatic diamines afforded a series of bis(glycosylamino)alkanes and-arenes. A possible mechanism
was proposed for the formation of 1,2-bis(β-D-glycosylamino)benzenes.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2793–2801, December, 2005. 相似文献
Aqua magnesium phthalocyanine bis(diethylamine) complex was obtained in the crystalline form and its crystal structure was determined by single-crystal X-ray diffraction. The Mg atom is 4 + 1 coordinated by four N isoindole atoms and one O atom. The MgPc moiety is non-planar, the Mg(II) is deviated by 0.492(2) Å from the N4-isoindole plane towards the oxygen atom of water molecule. The arrangement of MgPc(H2O) and diethylamine molecules is determined by O–HN hydrogen bonds and π–π interactions. The complex is stable up to 140 °C. At this temperature the complex loses diethylamine molecules and next at 200 °C loses the water molecule and finally converts into β-MgPc. 相似文献
The reaction of bis(triphenylgermyl)cadmium with nickelocene proceeds through the displacement of a cyclopentadienyl ring and the formation of an organopolymetallic compound containing nine metal atoms: This is a new type of organometallic compound, containing NiCd bonds. 相似文献
The compound 3,3'-(anthracene-9,10-diyl)bis(1-phenylpropan-1-one)(C32H26O2,Mr=442.55) has been synthesized by the reaction of 2,2'-(anthracene-9,10-diylbis(methy-lene))bis(1,3-diphenylpropane-1,3-dione) with CsCO3,and its structure was characterized by 1H NMR and single-crystal X-ray diffraction.The crystal of the title compound belongs to monoclinic,space group P21/c with a=9.154(3),b=5.2777(16),c=24.897(7) nm,β=107.337(10)°,Z=2 and V=1.1482 nm3.X-ray analysis indicates that an intermolecular hydrogen bond C(8)-H(8A)…O(1),weak C-H···π between H(9A) and the centre of anthracene rings and weak π-π interactions between two anthracene ring planes are observed. 相似文献
The title ring-bridged bis(cyclopentadienyl)diiron complexes [η5,η5-C5H4–Si(SiMe3)2–C5H4]Fe2(CO)L(μ-CO)2 [L = CO (1), P(OPh)3 (2), P(OMe)3 (3), PPh3 (4), PMe3 (5)] that contain exocyclic Si–Si bonds attached to the bridging silicon atom have been synthesized. The Si–Si bonds were found to be stable to the intramolecular iron centers under both thermal and photochemical conditions, in sharp contrast to the facile cleavage of the Si–Si bond in 1,1,2,2-tetramethyldisilanylene-bridged analogous complexes. The stability of the Si–Si bonds in the present cases may be attributed to the fact that these Si–Si bonds are spatially unapproachable by the intramolecular coordinatively unsaturated iron centers. Molecular structures of 1 and 2 have been determined by X-ray diffraction methods. An obvious conformational change due to substitution of CO for P(OPh)3 was observed. 相似文献
The complex H2Ru(PPh3)4 reacts with methyl acrylate to give bis(methylacrylate)bis(triphenylphosphane)ruthenium(0). Temperature-dependent NMR spectra show that the complex exists in two isomeric forms in solution. The major form (ca. 74%) has one methyl acrylate ligand η2-coordinated and the other η4 -coordinated as a 1-oxabutadiene ligand. This complex reacts with water to give the monoaqua adduct, the crystal structure of which is reported. 相似文献
Summary A mixed metal oxalate, manganese(II)bis(oxalato)nickelate(II)tetrahydrate, has been synthesized and characterized by elemental analysis, IR spectral and X-ray powder diffraction (XRD) studies. Thermal decomposition studies (TG, DTG and DTA) in air showed that the compound decomposed mainly to Mn2O3, MnO2 and NiO at ca.1000°C, via. the formation of several intermediates. DSC study in nitrogen upto 500°C showed the endothermic decomposition. The tentative mechanism for the thermal decomposition in air is proposed. 相似文献
Two new cobalt (II) and cobalt (III) complexes of a terpyridine based ligand, (4′-(2-thienyl)-2,2′;6′,2″-terpyridine (L)), were synthesized. Each complex has two units of the tridentate ligand. The complexes were fully characterized by spectroscopic methods as well as CHN analysis. Moreover, their solid state structures were determined by single crystal X-ray diffraction. The cobaltous complex has the formula [Co(L)2](NO3)2·2CH3OH·H2O (1), whereas the cobaltic complex shows the formula [Co(L)2](NO3)3·2CH3OH (2). Both complexes were tested as homogenous catalysts for the oxidation of a variety of aliphatic and aromatic alcohols utilizing aqueous hydrogen peroxide in water media. The Co(II) complex showed more activity in comparison with its isostructural Co(III) species. The results show that the aromatic alcohols were oxidized with higher conversions and selectivity compared to the aliphatic substrates, possibly due to their conjugation systems which thermodynamically stabilized the carbonyl products. 相似文献
Single crystals of bis (glycine) lithium molybdate [BGLM] with dimensions 20 mm × 10 mm × 5 mm were grown by slow evaporation technique. The grown crystals were subjected to powder X-ray diffraction studies. Functional groups of the crystallized molecules were confirmed by FTIR analyses. Transmission range of the crystal was determined by UV–vis–NIR spectra. Vickers microhardness test was performed on the prominent plane (0 1 1) of the grown crystal. The NLO property of the crystal was confirmed by Kurtz SHG test and compared with NLO efficiency of KDP crystal. 相似文献
The preparation of the barium β-diketonate complexes with crown-ethers [Ba(pta)2(18-crown-6)] (1), [Ba(pta)2(18-crown-6)] (THF) (2), [Ba(pta)2(18-dibenzocrown-6)](C6H5CH3) (3), [Ba(pta)2(18-dibenzocrown-6)] (4) (pta = 1,1,1-trifluoro-5,5-dimethylhexanedionato-2,4; 18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane; 18-dibenzocrown-6 = 6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]-hexaoxacyclooctadecane) is described. The complexes 1 and 2 have been synthesized from reaction of metallic barium with 2 molar equiv. of Hpta and 1 molar equiv. of 18-crown-6 in toluene; the complexes 3 and 4 from reaction of Ba(OH)2·8H2O with 1 molar equiv. 18-dibenzocrown-6 and 2 molar equiv. Hpta. The complexes were characterized by elemental analyses, IR-spectroscopy, 1H NMR spectroscopy. The crystal structures of 2 and 3 were determined by means of single-crystal X-ray diffraction methods. A single-crystal X-ray study of 2 and 3 has shown it be monomeric. The coordination number of Barium cation in 2 and 3 is nine owing to nine oxygen atoms from two pta ligands and crown-ether molecule. 相似文献
Zinc salt of mono(hydroxypentyl)phthalate, Zn(HPP)2, was synthesized by reacting 1,5-pentanediol, phthalic anhydride and zinc acetate. Zinc-containing poly(urethane-ether)s (PUEs) were synthesized by reacting hexamethylene diisocyanate (HMDI) or toluene 2,4-diisocyanate (TDI) with a mixture of Zn(HPP)2 and poly(ethylene glycol) (PEG300 or PEG400) in dimethylsulfoxide (DMSO) at 95 °C under nitrogen atmosphere using di-n-butyltin dilaurate as a catalyst. Blank PUEs without Zn(HPP)2 were also prepared by reacting PEG300 or PEG400 with HMDI or TDI under similar conditions. The structure of the polymers was confirmed by FT-IR, 1H NMR, 13C NMR, and solid-state 13C-CP-MAS NMR spectra. The zinc-containing polymers were soluble in only highly polar solvents. The inherent viscosity of the zinc-containing PUEs was found to be very low. X-ray diffraction studies revealed that HMDI-based (PUEs) were partially crystalline while TDI based (PUEs) were amorphous. The Tg values of the zinc-containing PUEs were found to be low and range from 5.3 to 7.5 °C. The thermogravimetric analysis revealed the influence of zinc on the initial decomposition and the overall thermal stability of the polymers. 相似文献
Reaction between bis(chlorodiphenylstanyl)methane and the sodium salt of 2-hydroxypyridine (pyONa) in the molar ratio of 1:2 provides the organotin hydroxide derivative [Ph2(pyO)SnCH2Sn(OH)Ph2]2 (1) (where pyO = anion of 2-hydroxypyridine), while reaction of bis(dibromophenylstanyl)methane with the sodium salt of pyrimidine-2-thione (pmtNa) in molar ratio of 1:4 gives the corresponding organotin thiolate derivative, as its toluene solvate [BrPh(pmt)Sn]2CH2 · C7H8 (2) (where pmt = anion of pyrimidine-2-thione). Both compounds were characterized by single crystal X-ray diffraction analysis and contain five-coordinate tin atoms. Compound 1 is a centrosymmetric head-to-tail dimmer with almost symmetrical Sn(1)-O(H)-Sn(2A) bridges. 相似文献
The complex cis-Pt(Ph3Ge)2(PMe2Ph)2 underwent smooth isomerization to give the trans-isomer at room temperature via an associative five-coordinated intermediate. Thermodynamic parameters and activation energy for the cis to trans isomerization were obtained, ΔH# = 105 kJ mol−1, ΔS# = 12.5 J mol−1 K−1, and Ea = 107 kJ mol−1, respectively. Heating of trans-Pt(Ph3Ge)2(PMe2Ph)2 at 50 °C for 36 days produced trans-PtPh(Ph3Ge)(PMe2Ph)2 followed by the formation of trans-PtPh2(PMe2Ph)2, Pt(PMe2Ph)4, and Ph4Ge finally via elimination of the phenyl group from Ph3Ge ligand with liberation of the Ph2Ge unit and subsequent reductive elimination of the remaining Ph3Ge ligand at 80 °C for 1 month. 相似文献
Conclusions This is the first report of the synthesis of a 3,4-bis(pyrimidyl)furoxane by the oxidation of bis (pyrimidyl)glyoxime. The substrate used was 1,2-bis(2,4-diethoxypyrimidin-6-yl) glyoxime.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 915–917, April, 1988.Deceased. 相似文献