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Title: Synthesis and structure of the new binuclear complex eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe-eta/sup 1/-C/sub 5/H/sub 4/(CO)/sub 2/Fe-CH/sub 3/ (in Russian)

Abstract

The authors have found that the dimeric complex (eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe)/sub 2/ is also metallated in the cyclopentadiene ring under these conditions, although the yield of the product from the decomposition of the lithium derivative with heavy water (the monodeuterated derivative) does not exceed 20%. During an attempt to use the metallation of (eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe)/sub 2/ to produce the methyl-substituted complex eta/sup 5/CH/sub 3/C/sub 5/H/sub 4/-eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 4/Fe/sub 2/ the binuclear complex eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe-eta/sup 1/-C/sub 5/H/sub 4/(CO)/sub 2/Fe-CH/sub 3/ (I) was obtained instead of the expected product. It can be supposed that the butyllithium used as metallating agent is capable of reducing the dimer with the formation of the (eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe)/sup -/ anion. With the addition of the electrophilic agent methyl iodide this anion gives the sigma-methyl derivative eta/sup 5/-C/sub 4/H/sub 6/(CO)/sub 2/FeCH/sub 3/, which is metallated in the cyclopentadiene ring by an excess of butyllithium. The obtained lithium derivative eta/sup 4/-LiC/sub 5/H/sub 4/(CO)/sub 2/Fe-CH/sub 3/ reacts with eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/FeI, which was also found among the reaction products, giving the binuclear complex (I). In order to check this suggestion the authors realized the metallationmore » of the authentic eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe-CH/sub 3/ with butyllithium in THF at -78/sup 0/C; with the subsequent addition of eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/FeI to the reaction mixture they in fact obtained compound (I).« less

Authors:
; ; ;
Publication Date:
Research Org.:
A.N. Nesmeyanov Institute of Heteroorganic Compounds, Moscow, USSR
OSTI Identifier:
6416836
Resource Type:
Journal Article
Journal Name:
Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States)
Additional Journal Information:
Journal Volume: 35:2; Other Information: Translated from Izvestiya Akademii Nauk SSSR Seriya Khimicheskaya, 35: No. 4, 437-440(Feb 1986)
Country of Publication:
United States
Language:
Russian
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; IRON COMPLEXES; STRUCTURAL CHEMICAL ANALYSIS; SYNTHESIS; LITHIUM COMPLEXES; CATALYTIC EFFECTS; BOND ANGLE; BOND LENGTHS; CARBONYLS; COMPLEXOMETRY; CYCLOPENTADIENE; DEUTERIUM COMPOUNDS; DIMERS; ELECTRON SPIN RESONANCE; ELECTRONIC STRUCTURE; INFRARED SPECTRA; LIGANDS; MASS SPECTRA; MONOCLINIC LATTICES; TETRAHYDROFURAN; X-RAY DIFFRACTION; ALKENES; COHERENT SCATTERING; COMPLEXES; CRYSTAL LATTICES; CRYSTAL STRUCTURE; CYCLOALKENES; DIENES; DIFFRACTION; DIMENSIONS; FURANS; HETEROCYCLIC COMPOUNDS; HYDROCARBONS; HYDROGEN COMPOUNDS; LENGTH; MAGNETIC RESONANCE; ORGANIC COMPOUNDS; ORGANIC OXYGEN COMPOUNDS; POLYENES; RESONANCE; SCATTERING; SPECTRA; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties; 360602 - Other Materials- Structure & Phase Studies

Citation Formats

Orlova, T Yu, Setkina, V N, Andrianov, V G, and Struchkov, Yu T. Synthesis and structure of the new binuclear complex eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe-eta/sup 1/-C/sub 5/H/sub 4/(CO)/sub 2/Fe-CH/sub 3/. United States: N. p., 1986. Web. doi:10.1007/BF00952936.
Orlova, T Yu, Setkina, V N, Andrianov, V G, & Struchkov, Yu T. Synthesis and structure of the new binuclear complex eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe-eta/sup 1/-C/sub 5/H/sub 4/(CO)/sub 2/Fe-CH/sub 3/. United States. https://doi.org/10.1007/BF00952936
Orlova, T Yu, Setkina, V N, Andrianov, V G, and Struchkov, Yu T. 1986. "Synthesis and structure of the new binuclear complex eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe-eta/sup 1/-C/sub 5/H/sub 4/(CO)/sub 2/Fe-CH/sub 3/". United States. https://doi.org/10.1007/BF00952936.
@article{osti_6416836,
title = {Synthesis and structure of the new binuclear complex eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe-eta/sup 1/-C/sub 5/H/sub 4/(CO)/sub 2/Fe-CH/sub 3/},
author = {Orlova, T Yu and Setkina, V N and Andrianov, V G and Struchkov, Yu T},
abstractNote = {The authors have found that the dimeric complex (eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe)/sub 2/ is also metallated in the cyclopentadiene ring under these conditions, although the yield of the product from the decomposition of the lithium derivative with heavy water (the monodeuterated derivative) does not exceed 20%. During an attempt to use the metallation of (eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe)/sub 2/ to produce the methyl-substituted complex eta/sup 5/CH/sub 3/C/sub 5/H/sub 4/-eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 4/Fe/sub 2/ the binuclear complex eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe-eta/sup 1/-C/sub 5/H/sub 4/(CO)/sub 2/Fe-CH/sub 3/ (I) was obtained instead of the expected product. It can be supposed that the butyllithium used as metallating agent is capable of reducing the dimer with the formation of the (eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe)/sup -/ anion. With the addition of the electrophilic agent methyl iodide this anion gives the sigma-methyl derivative eta/sup 5/-C/sub 4/H/sub 6/(CO)/sub 2/FeCH/sub 3/, which is metallated in the cyclopentadiene ring by an excess of butyllithium. The obtained lithium derivative eta/sup 4/-LiC/sub 5/H/sub 4/(CO)/sub 2/Fe-CH/sub 3/ reacts with eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/FeI, which was also found among the reaction products, giving the binuclear complex (I). In order to check this suggestion the authors realized the metallation of the authentic eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe-CH/sub 3/ with butyllithium in THF at -78/sup 0/C; with the subsequent addition of eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/FeI to the reaction mixture they in fact obtained compound (I).},
doi = {10.1007/BF00952936},
url = {https://www.osti.gov/biblio/6416836}, journal = {Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States)},
number = ,
volume = 35:2,
place = {United States},
year = {Wed Aug 20 00:00:00 EDT 1986},
month = {Wed Aug 20 00:00:00 EDT 1986}
}