Insertion of nitriles into complexes of tantalum pentachloride with amines

Title: Insertion of nitriles into complexes of tantalum pentachloride with amines

Full Record
Other Related Research

Abstract

Data from the study of the insertion of aceto-, propio-, and benzonitrile into complexes of TaCl/sub 5/ with diethyl- and triethylamine in CCl/sub 4/ solutions have been discussed. It has been established that the nature of the ligands, rather than the nitrile being inserted into the complex, has a significant influence on the composition of the final products. In contrast to the case of acetonitrile, the insertion of propionitrile and benzonitrile into a complex is observed already at room temperature. On the basis of spectroscopic data it has been postulated that the carbon tetrachloride employed as a solvent accelerates the insertion of nitriles and promotes their deprotonation in the presence of an aprotic amine.

Authors:: Glushkova, M A; Chumaevskii, N A; Khmelevskaya, L V; Ershova, M M; Buslaev, Yu A

Publication Date:: 1988-01-01

Research Org.:: N. S. Kurnakov Institute of General and Inorganic Chemistry (USSR)

OSTI Identifier:: 6616420

Resource Type:: Journal Article

Journal Name:: Sov. J. Coordinat. Chem.; (United States)

Additional Journal Information:: Journal Volume: 13:3; Other Information: Translated from Koordinatsionnaya Khimiya; 13: No. 3, 349-353(Mar 1987)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMINES; ISOMERIZATION; NITRILES; TANTALUM COMPLEXES; ACETONITRILE; CARBON TETRACHLORIDE; COMPLEXOMETRY; INFRARED SPECTRA; PROPIOLONITRILE; RAMAN SPECTRA; SOLVENT PROPERTIES; SYNTHESIS; TANTALUM CHLORIDES; VIBRATIONAL STATES; CHEMICAL REACTIONS; CHLORIDES; CHLORINATED ALIPHATIC HYDROCARBONS; CHLORINE COMPOUNDS; COMPLEXES; ENERGY LEVELS; EXCITED STATES; HALIDES; HALOGEN COMPOUNDS; HALOGENATED ALIPHATIC HYDROCARBONS; ORGANIC CHLORINE COMPOUNDS; ORGANIC COMPOUNDS; ORGANIC HALOGEN COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; REFRACTORY METAL COMPOUNDS; SPECTRA; TANTALUM COMPOUNDS; TRANSITION ELEMENT COMPLEXES; TRANSITION ELEMENT COMPOUNDS; 400201* - Chemical & Physicochemical Properties

Citation Formats


                    Glushkova, M A, Chumaevskii, N A, Khmelevskaya, L V, Ershova, M M, and Buslaev, Yu A. Insertion of nitriles into complexes of tantalum pentachloride with amines.  United States: N. p., 1988. 
        Web.

Copy to clipboard


                    Glushkova, M A, Chumaevskii, N A, Khmelevskaya, L V, Ershova, M M, & Buslaev, Yu A. Insertion of nitriles into complexes of tantalum pentachloride with amines.  United States.

Copy to clipboard


                    Glushkova, M A, Chumaevskii, N A, Khmelevskaya, L V, Ershova, M M, and Buslaev, Yu A. Fri .  
        "Insertion of nitriles into complexes of tantalum pentachloride with amines".  United States.

Copy to clipboard


                    
@article{osti_6616420,

  title        = {Insertion of nitriles into complexes of tantalum pentachloride with amines},

  author       = {Glushkova, M A and Chumaevskii, N A and Khmelevskaya, L V and Ershova, M M and Buslaev, Yu A},

  abstractNote = {Data from the study of the insertion of aceto-, propio-, and benzonitrile into complexes of TaCl/sub 5/ with diethyl- and triethylamine in CCl/sub 4/ solutions have been discussed. It has been established that the nature of the ligands, rather than the nitrile being inserted into the complex, has a significant influence on the composition of the final products. In contrast to the case of acetonitrile, the insertion of propionitrile and benzonitrile into a complex is observed already at room temperature. On the basis of spectroscopic data it has been postulated that the carbon tetrachloride employed as a solvent accelerates the insertion of nitriles and promotes their deprotonation in the presence of an aprotic amine.},

  doi          = {},

  url          = {https://www.osti.gov/biblio/6616420},
  journal      = {Sov. J. Coordinat. Chem.; (United States)},
number       = ,

  volume       = 13:3,

  place        = {United States},

  year         = {1988},

  month        = {1}

}

Copy to clipboard

Journal Article:

Other availability

Find in Google Scholar

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Gas Phase Computational Studies on the Competition Between Nitrile and Water Ligands in Uranyl Complexes

Journal Article Schoendorff, George E ; De Jong, Wibe A ; Gordon, Mark S ; ... - Journal of Physical Chemistry A, 114(33):8902-8912

The formation of uranyl dicationic complexes containing water and nitrile (acetonitrile, propionitrile, and benzonitrile) ligands, [UO2(H2O)n(RCN)m]2+, has been studied using density functional theory (DFT) with a relativistic effective core potential (RECP) to account for scalar relativistic effects on uranium. It is shown that nitrile addition is favored over the addition of water ligands. Decomposition of these complexes to [UO2OH(H2O)n(RCN)m]+ by the loss of either H3O+ or (RCN+H)+ is also examined. It is found that this reaction occurs when the coordination sphere of uranyl is unsaturated. Additionally, this reaction is influenced by the size of the nitrile ligand with reactions involvingmore » acetonitrile being the most prevalent.« less
https://doi.org/10.1021/jp103227x
Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives

Journal Article Schoendorff, George E ; Windus, Theresa L ; De Jong, Wibe A - Journal of Physical Chemistry A, 113(45):12525-12531

The coordination of nitrile (acetonitrile, propionitrile, and benzonitrile) and carbonyl (formaldehyde, ethanal, and acetone) ligands to the uranyl dication (UO22+) has been examined using density functional theory (DFT) utilizing relativistic effective core potentials (RECPs). Complexes containing up to six ligands have been modeled for all ligands except formaldehyde, for which no minimum could be found. A comparison of relative binding energies indicates that five coordinate complexes are predominant while a six coordinate complex involving propionitrile ligands might be possible. Additionally, the relative binding energy and the weakening of the uranyl bond is related to the size of the ligand and,more »« less
https://doi.org/10.1021/jp9038623
Nucleophilic addition of nitriles to secondary terpene alcohols

Journal Article Kozlov, N G ; Popova, L A ; Nesterov, G V - J. Gen. Chem. USSR (Engl. Transl.); (United States)

The addition of nitriles of varying nucleophilicity to isocamphanol and exo-1,5,5-trimethyl-bicyclo(2.2.1)heptan-2-ol (isofenchol) was investigated. The authors examined the effect of the reaction conditions on the yield and structure of the target products of the reaction: N-substituted amides. As a result of the study, it was shown that in the reaction with chloroacetonitrile, propionitrile, methoxypropionitrile, isovaleronitrile, and phenylacetonitrile under the conditions of the Ritter reaction, isocamphanol is transformed into the corresponding substituted exo-N-acyl-1,7,7-trimethylbicyclo(2.2.1)hept-2-ylamines, as in the reaction with aceto- and benzonitriles, due to 2,6-hydride displacement accompanied by Wagner-Meerwein rearrangement. The structures of these amides were demonstrated by PMR spectroscopy.
RADIATION MEASUREMENTS--COMPARISON OF RADIOLYSIS EFFECTS OF COBALT-60 GAMMA RAYS AND 3-6 Mev ELECTRONS ON NITRILE SYSTEMS

Thesis/Dissertation Miller, G H

The object of this investigation was to develop a liquid chemical dosimeter, useful in the dose range from 10/sup 6/ through 10/sup 8/ rads or above, using nitriles; to determine the type and yield of radiolysis products of the nitriles; and to determine whether the high instantaneous dose rate of electrons from it pulsed linear accelerator has a radiolysis effect different from that of gamma radiation from Co/sup 60/ as measured by changes in dosimeter products. High intensity gamma-ray and accelerated electron sources require liquid chemical dosimeters in the 10/sup 6/-10/sup 8/ rad range for accurate dose measurement of intendedmore »« less
Environmentally Benign and Scalable Preparation of Diethyl Furoxan-3,4-dicarboxylate Using Silver Carbonate as a Nitrile Oxide Generator

Journal Article Zhang, Mao-Xi ; DeHope, Alan J. ; Pagoria, Philip. F. - Organic Process Research & Development

Diethyl furoxan-3,4-dicarboxylate (1) is a starting material for many heterocyclic compounds containing furoxan and furazan rings. Usually, furoxan 1 was prepared via a dimerization of corresponding nitrile oxide generated either by treatment of ethyl 2-chloro-2-(hydroxyimino)-acetate (2) with triethylamine or by nitration or conversion of α-activated ethyl acetate with acetyl nitrate in acetic acid or other catalytic reagents. Both methods are suitable for small-scale but suffered from various drawbacks for large-scale preparation. Years ago, a general method for the preparation of furoxan from corresponding hydroximidoyl chloride (R–CCl=NOH) with silver carbonate (Ag ₂CO ₃) was developed in our group. Now this methodmore »« less
Cited by 1
https://doi.org/10.1021/acs.oprd.9b00228

Full Text Available

Similar Records