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1.
L.I. Denisovich N.V. Zakurin A.A. Bezrukova S.P. Gubin 《Journal of organometallic chemistry》1974,81(2):207-216
The products of chemical and electrochemical oxidation of metallocenes, (C5H5)2M (M Fe, Ru, Os), were investigated. (C5H5)2Fe on Pt and Hg anodes was oxidized to the ferricenium cation while the electrolysis of osmocene on Pt electrode led to the previously unknown (C5H5)2OsoBF4? salt and oxidation of ruthenocene yielded the unstable (C5H5)2Ru2+ cation. On a mercury electrode Ru and Os metallocenes gave the adducts [(C5H5)2M]2Hg(BF4)2. The stability constants of mercury-containing complexes were calculated using the polarographic data. The chemical interaction of metallocenes with HgX2 also gave mercury-containing adducts. Chemical oxidation of ruthenocene resulted in salts with the metal in the +4 formal oxidation state. 相似文献
2.
I. S. Ignat’ev D. V. Vrazhnov T. A. Kochina 《Russian Journal of General Chemistry》2010,80(7):1283-1287
Equilibrium structures of the isomers and transition states of their interconversion in the system C4H11M+ (M = Si, Ge) have been obtained at theB3LYP level of theory using the cc-pVTZ basis set. The structures of these stationary
points are close for Si and Ge; the most stable isomer in both systems is the tertiary cation (C2H5)(CH3)2M+, the second in energy is complex with ethylene [(CH3)2HM·C2H4]+. The secondary cation (C2H5)2HM+ is third in energy isomer, the height of the barrier of interconversion for these three cations being practically independent
on M. However, for M = Ge a substantial decrease in the energy of isomeric forms corresponding to complexes with alkanes is
observed. As a result, in the system C4H11Ge+ the fourth in energy is isomer [(C2H5)Ge·C2H6]+ rather than [(C2H5)H2Ge·C2H4]+ as for M = Si. Nevertheless, the height of the barriers for transition into these structures, although decreasing from M
= Si to Ge, remain rather high, and the most favorable route of decomposition in both systems is the elimination of ethylene. 相似文献
3.
Contributions to the Chemistry of Organo Transition Metal Compounds. 55. Preparation and Properties of Niobocenium and Tantalocenium Salts — Crystal and Molecular Structure of [(C5H5)2NbCl2][BF4] · CH3CN Niobocenium and tantalocenium compounds of the type [(C5H5)2MCl2]X (X = BF4, PBh4, PF6) were synthesized from the metallocene dichlorides and ferricenium salts, [(C5H5)2Fe]X, in methylene dichloride or tetrahydrofuran. With acetonitrile as solvent [(C5H5)2MCl2]X · CH3CN complexes are formed. Stable methyl compounds of the type [(C5H5)2M(CH3)2]X were obtained, when (C5H5)2Ta(CH3)2 is oxidized by means of ferricenium salts. The new complexes were characterized by elemental analysis, i. r., and 1H n.m.r. spectra. The structure of [(C5H5)2NbCl2][BF4] · CH3CN has been determined by X-ray structure analysis. The compound crystallizes in the orthorhombic space group Cmcm with a = 8.324(12), b = 19.581(13), c = 9,563(8) Å and Z = 4. The coordination geometry of the Nb atom is tetrahedrally. 相似文献
4.
Ying Peng Shaofang Lu Daxu Wu Qiangjin Wu Jianquan Huang 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(5):e183-e184
The crystal structure of the title complex, (C8H10N)2(C5H6N)[BiI6], contains discrete [BiI6]3? anions, and (HNC5H5)+ and (CH3COCH2NC5H5)+ cations separated by normal van der Waals contacts. The [BiI6]3? anion has the Bi atom on an inversion centre. The (HNC5H5)+ cation also lies about an inversion centre and is disordered. The (CH3COCH2NC5H5)+ cation lies in a general position. 相似文献
5.
Metal Complexes of Biologically Important Ligands. CXVII [1] Addition of the O'Donnell Reagent [Ph2C=NCHCO2Me]– to Coordinated, Unsaturated Hydrocarbons of [(C6H7)Fe(CO)3]+, [C7H9Fe(CO)3]+, [(C7H7)M(CO)3]+ (M = Cr, Mo), and [(C2H4)Re(CO)5]+. α-Amino Acids with Organometallic Side Chains The addition of [Ph2C=NCHCO2Me]– to [(C6H7)Fe(CO)3]+, [(C7H9)Fe(CO)3]+, [(C7H7)M(CO)3]+ (M = Cr, Mo) and [(C2H4)Re(CO)5]+ gives derivatives of α-amino acids with organometallic side chains. The structure of [(η4-C6H7)CH(N=CPh2)CO2Me]Fe(CO)3 was determined by X-ray diffraction. From the adduct of [Ph2C=NCHCO2Me]– and [(C7H7)Mo(CO)3]+ the Schiff base of a new unnatural α-amino acid, Ph2C=NCH(C7H7)CO2Me, was obtained. 相似文献
6.
Reactions of CH3Li, C6H5Li, and C6H5CH2MgCl with [(C5H5)Fe(CO)2Y]+-[B(C6H5)4]− [Y Co, P(C6H5)3, and CS] have been investigated. The organolithium reagents used act either as reducing agents or as nucleophilic reagents towards the cyclopentadienyliron tricarbonyl cation and its thiocarbonyl analogue. Benzyl-magnesium chloride reacts with the cyclopentadienyl ring of [(C5H5)Fe(CO)3]+ and [(C5H5)Fe(CO)2P(C6H5)3]+ producing neutral cyclopentadiene complexes. 相似文献
7.
D. Naoufal P. Selucký B. Grüner B. Bonnetot H. Mongeot 《Journal of Radioanalytical and Nuclear Chemistry》2005,266(1):145-148
Summary New anion derivatives of the closo-decaborate [B10H10]2- bearing amine or phosphine groups were tested for the extraction of radioactive cesium cations in acidic medium. The technique used is the liquid-liquid extraction based on the complexation of Cs+ by these anions to form neutral compounds which are extracted by organic solvents (diluents) of medium polarity. Promising results were obtained with the anion [1-(C6H5CH2)2(C6H5)NB10H9]- (3) soluble in many organic solvents. The most efficient diluent for the extraction is nitrobenzene. Using hydrochloric acid or sulfuric acid in the aqueous medium instead of nitric acid does not significantly affect the efficiency of Cs+ extraction. 相似文献
8.
S. G. Semenov Yu. F. Sigolaev A. V. Belyakov 《Russian Journal of General Chemistry》2006,76(11):1729-1731
Calculations by the PCM/B3LYP/6-311G++(3d5f7)&;Xe-3-111G(3d5)PCM/B3LYP/6-311G-(3d5f7)&;Xe-3-111G(d5) method show that, despite the higher electronegativity of the nitrogen atom, the interaction between the CN? anion and the (pentaphenyl)xenonium(II) cation forms a xenon-carbon bond which is stronger by 6 kcal mol?1 than the direct ionic bond between CN? and Xe+. 相似文献
9.
In continuation of our studies in the new area of multiple photon laser dissociation of ions, we report evidence for the sequential two photon dissociation of cyanobenzene radical cation, C6H5CN+, to produce predominantly C6H+4 and HCN. The complete excitation function for this process, as well as for a single photon process occurring at higher energies, are compared to the photoelectron spectrum of cyanobenzene to elucidate the nature of the transitions involved. An exact kinetic expression is derived and used to obtain information about the absorption spectra of C6H5CN+ in its ground vibronic state and with internal energy between 2.0 and 2.8 eV. Finally, data from our earlier study of benzene radical cation is reanalyzed and discussed. 相似文献
10.
The complexes of the type (ArCH2)2SnO were catalytic-oxygenated by Ag+ and yielded mixed-ligand organotin(IV) complexes (ArCH2)(2-C5H4NCO2)2(ArCOO)tin(IV) (Ar = C6H5 (1), 2-ClC6H4 (2), 2-CNC6H4 (3), 4-ClC6H4 (4), 4-CNC6H4 (5), 2-FC6H4 (6)). The complexes 1-6 are characterized by elemental analyses, IR and NMR (1H, 13C, 119Sn) spectroscopies. Single X-ray crystal structure analysis has been determined, which reveals that the center tin atom of complex 2 is seven-coordinated geometry. 相似文献
11.
M.B. Huang 《Tetrahedron》1985,41(22):5209-5212
The electronic structures of five C9H9-, carboanions have been studied by ab initio STO-3G calculations, and some general conclusions on related C9H9- and C9H9+ structures are presented. Large antibonding interactions in one occupied MO make barbaral-9-yl anion (2) unstable as its cationic counterpart (8). The proposed D9h-symmetrical cation and D3h-symmetrical anion (3) do not exist due to Jahn-Teller distortions. A study of the MO correlations confirms that the two tetracyclic anions with C2v symmetry (5 and 6) are the results of the Jahn-Teller distortions of 3. Anion 5 is identified as the proper intermediate of the Cope rearrangement of anion 2. 相似文献
12.
《Journal of organometallic chemistry》1986,304(3):341-351
The use of ferricenium cations [(C5H5)2FE]X (X = BF4, PF6, SbF6) as one-electron oxidizing agents for organometallic complexes is demonstrated. Sandwich compounds M(C5H5)2 (M = Cr, Co, Ni) and Cr(C6H6)2 are oxidized in nearly quantitative yield to the corresponding cations [M(C5H5)2]BF4 and [(C6H6)2Cr]BF4. The metalmetal bond in the dinuclear organometallic complexes [DienylM(CO)n]2 (M = Mo (n = 3), Fe (n = 2), Ni (n = 1)) and Co2(CO)8 is fissioned by (C5H5)2Fe+ in the presence of neutral ligands L to form the corresponding cationic compounds [DienylM(CO)nLm]X (M = Mo (n = 2), Fe (n = 2), Ni (n = 0)) and [Co(CO)3L2BF4 (L = VB and VIB donor ligands) in high yields.The practical applications of ferricenium cations are discussed in comparison with other methods for the preparation of cationic organometallic complexes. 相似文献
13.
The reactions of arenediazomolybdenum(II) complexes such as [(η-C5H5)Mo(N2C6H4CH3-p)I2]2, (η-C5H5)Mo(CO species with neutral and anionic monodentate or chelating ligands have been investigated. The new arenediazo complexes isolated from these reactions include neutral species such as (η-C5H5)Mo(PPh3)(N2C6H4CH3-p)I2 and (η-C5H5)Mo(N2C6H4CH3-p) cations of the type [η-C5H5)Mo(bipy)(N2C6H4CH3-p)I]+ and the anion [(η-C5H5)Mo(N2C6H4CH3-p)I3]?. The structures of the new complexes are discussed. 相似文献
14.
Characterization of Distortional Isomers of the Anions Pentacyano-oxo-molybdate(IV) and of Tetracyano-aqua-oxo-molybdate(IV) in the Solid State. Crystal Structures of [(C6H5)4P]3[MoO(CN)5] · 7 H2O (green), [(C6H5)4As]2[MoO(OH2)(CN)4] · 4 H2O (blue), and [(C6H5)4P]2[MoO(OH2) (CN)4] · 4 H2O (green) Preparation of a series of salts containing the new pentacyano-oxo-molybdate(IV) anion is described: Cs2H[MoO(CN)5] (blue), [(CH3)4N]2H[MoO(CN)5] · 2 H2O (blue) and [Cr(en)3] [MoO(CN)5] · 4 H2O (green). The green [(C6H5)4P]3[MoO(CN)5] · 7 H2O crystallizes triclinic in the space group P1 . The molybdenum(IV) center is in an pseudo-octahedral environment of a terminal oxo-group (d(Mo?O); 1.705(4) Å), a CN? group in the trans-position (d(Mo? C): 2.373(6) Å), and four equatorial CN? groups (averaged d(Mo? C): 2.178 (Å). The blue and green salts exhibit v(Mo?O) stretching frequencies at 948 cm?1 and 920 cm?1, respectively. Blue and green salts containing the [MoO(OH2)(CN)4]2? anion and [(C6H5)4P]+ or [(C6H5)4As]+ cations have been prepared and characterized by single crystal crystallography. [(C6H5)4P]2[MoO(OH2)(CN)4] · 4 H2O (green) and [(C6H5)4As]2[MoO(OH2)(CN)4] · 4 H2O (blue) crystallize monoclinic in the space group C—P21/n. They are considered to be distortional isomers of the complex anion: the green species has a Mo?O bond distance of 1.72(2) Å whereas for the blue species d(Mo?O) = 1.60(2) Å is found; the corresponding v(Mo?O) frequencies are at 920 cm?1 and 980 cm?1. 相似文献
15.
《Journal of membrane science》1998,146(1):9-13
Inorganic lithium permselective ion exchange membranes were prepared on a microporous alumina substrate by dip-coating solution containing Si(OC2H5)4, LiOC2H5, Mn(OC2H5)2 and C2H5OH. The membranes showed ion-selectivity for cation over anion and permselectivity for Li+ over Na+. The static transport number for cation [K+] is 0.75 and the permselectivity for Na+ over Li+ is 0.29, comparing 2.57 for ordinary organic ion exchange membrane. 相似文献
16.
Thomas M. Klaptke Burkhard Krumm Matthias Scherr 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(1):m17-m19
The title compounds, diaquadinitramidatolithium(I), [Li(N3O4)(H2O)2], (I), and pyridinium dinitramidate, C5H6N+·N3O4−, (II), differ significantly in their cation–anion contacts. The Li+ atom of (I) is coordinated by two O atoms of the dinitramide anion in a chelate and by four additional water molecules, with the Li and central N atom of the anion on a twofold rotation axis. The pyridinium cation of (II) exhibits a contact with the dinitramide anion via an intermolecular N—H...N hydrogen bridge. These interactions are compared with those found in reported anhydrous lithium dinitramide and ammonium dinitramide salts. 相似文献
17.
Frank Edelmann Peter Behrens Sabine Behrens Ulrich Behrens 《Journal of organometallic chemistry》1986,310(3)
Tricarbonyl(fulvene)chromium complexes react with anionic nucleophiles to give functionally substituted cyclopentadienyl derivatives. The nucleophilic attack occurs at the exocyclic carbon atom of the fulvene ligand. Addition of PPh2− to (η6-6,6-dimethylfulvene)Cr(CO)3 (1) yields the novel anion [(η5-C5H4C(CH3)2PPh2)Cr-(CO)3]−, which can be isolated as a K+, (C2H5)4N+, (C6H5)4P+, or Tl+ derivative (2–5). The potassium salt of the uncoordinated C5H4C(CH3)2PPh2− anion (7) is obtained by treatment of 6,6-dimethylfulvene with KPPh2·2C4H8O2. Similarly, NaC5H5 reacts with 1 to give Na[(η5-C5H4C(CH3)2C5H5)Cr(CO)3] (8). The reactions of (6-dimethylaminofulvene)Cr(CO)3 (15) with nucleophiles are accompanied by elimination of dimethylamine. Addition of Ph3P=CH2 to 15 gives an unstable product, but after reaction of 6-dimethylaminofulvene with Ph3P=CH2, the free ligand C5H4=CHCH=PPh3 (17) can be isolated in moderate yields. Deeply colored anions of the type [(η5:η5-C5H4C(R)=C5H4)Cr2(CO)6]− (R = H, N(CH3)2) are synthesized by reaction of 15 or (6-dimethylamino-6-methylthiofulvene)Cr(CO)3 with NaC5H5 and subsequent complexation of the mononuclear intermediate with (CH3CN)3Cr(CO)3. In addition, the synthesis of the new fulvene complexes [C5H4=CH(CH=CH)2N(CH3)Ph]M(CO)3 (23, 24; M = Cr, Mo) is described. The investigation is extended to α-ferrocenylcarbenium ions, which are isoelectronic with (fulvene)Cr(CO)3 complexes. [(η5-C5H5)Fe(C5H4CPh2)]+ BF4− (25) adds tertiary phosphines at the exocyclic carbon atom to give phosphonium salts of the type [(η5-C5H5)Fe(C5H4CPh2PR3)]+BF4−. A CO-substititution product of a tricarbonyl (fulvene)chromium complex is obtained for the first time by irradiation of (η6-6,6-diphenylfulvene)Cr(CO)3 in the presence of PPh3. In addition, an improved synthesis of the (CH3CN)3M(CO)3 complexes (M = Cr, Mo, W) is reported. 相似文献
18.
M. G. Voronkov A. A. Korlyukov V. S. Fundamenskii É.A. Zels’bst M. Yu. Antipin 《Journal of Structural Chemistry》2010,51(3):534-539
Two polymorphic modifications of N-methylbis(2-hydroxyethyl)ammonium hexafluorosilicate (AHFS) crystallize in monoclinic symmetry. The independent part of the unit cell of the low temperature modification contains two cations and an anion. The cell volume is two times smaller in the high temperature modification, the [SiF6]2- anion being disordered. In both modifications of methylbis(2-hydroxyethyl)ammonium hexafluorosilicate (HOCH2CH2)2HN+[SiF6]2-, the [SiF6]2- anion and the (HOCH2CH2)2HN+CH3 cation are linked by F…H—O hydrogen bonds. The silicon atom polyhedron in the anion is a tetragonal bipyramid; the coordination polyhedron of the nitrogen atom in the cation is a tetrahedron. 相似文献
19.
Kazuhiko Ohashi Masaharu Nishiguchi Yoshiya Inokuchi Hiroshi Sekiya Nobuyuki Nishi 《Research on Chemical Intermediates》1998,24(7):755-764
Electronic spectra of a homo-molecular dimer cation, (C6H5CN)2
+, are measured by photodissociation spectroscopy in the gas phase. Broad features appeared in the 450–650 nm region are characteristic
of π3 → πCN transitions of the C6H5CN+ chromophore. No intense band is observed in the 650–1300 nm region, where other aromatic dimer cations usually show charge
resonance bands. Two component molecules of (C6H5CN)2
+ cannot take a parallel sandwich configuration suitable for the resonance interaction, because of geometrical constraints
due to other stronger interactions. 相似文献
20.
M. S. Chernov’yants I. V. Burykin Z. A. Starikova A. A. Rassoshenko 《Russian Journal of Inorganic Chemistry》2016,61(2):217-220
Complexation in system 4-bromobenzyltriphenylphosphonium bromide–molecular iodine in chloroform has been studied. The limit number of iodine molecules coordinated by 4-bromobenzyltriphenylphosphonium bromide in solution and the stability constant of the complex have been determined by a spectrophotometric method using iodine average number functions. According to the X-ray diffraction data, the crystal structure of the charge transfer complex is formed by anion BrI2? and cation [(C6H5)3PCH2C6H4Br]+. In a crystal, translationally identical cations C25H21BrP+ form stacks along the y axis. Diiodobromide anions dimerized due to the I–I shortened contacts are located between the stacks. 相似文献