Reactions of co-ordinated ligands. Part 15. The cycloaddition of electronegatively substituted unsaturated systems to tricarbonyl(η-N-methoxycarbonyl-1H-azepine)-iron and -ruthenium and tricarbonyl(η-cyclohepta-2,4,6-trien-1-one)iron

Michael Green, Susan M. Heathcock, Terence W. Turney, D. Michael P. Mingos

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44 Citations (Scopus)

Abstract

Hexafluoroacetone, tetracyanoethylene, and 1,1 dicyano-2,2-bis(trifluoromethyl)ethyiene form exo-1,3 adducts with tricarbonyl(η-cyclohepta-2,4,6-trien-1-one)iron and tricarbonyl(η-N-methoxycarbonyl-1H-azepine)-iron and -ruthenium. A 1,6 adduct is also obtained with the azepineiron system. Deuteriation experiments show that the unco-ordinated double bond is the initial site of electrophilic attack. The 1,3-tetracyanoethylene adduct of the cycloheptatrienoneiron complex readily isomerises to a 1,5 adduct in solution. The generally accepted dipolar mechanism for these cycloaddition reactions is critically assessed and an alternative concerted reaction path is presented.

Original languageEnglish
Pages (from-to)204-211
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number2
DOIs
Publication statusPublished - 1 Dec 1977
Externally publishedYes

Cite this

@article{1c46fc13497e45d2a4151b11d0e841cd,
title = "Reactions of co-ordinated ligands. Part 15. The cycloaddition of electronegatively substituted unsaturated systems to tricarbonyl(η-N-methoxycarbonyl-1H-azepine)-iron and -ruthenium and tricarbonyl(η-cyclohepta-2,4,6-trien-1-one)iron",
abstract = "Hexafluoroacetone, tetracyanoethylene, and 1,1 dicyano-2,2-bis(trifluoromethyl)ethyiene form exo-1,3 adducts with tricarbonyl(η-cyclohepta-2,4,6-trien-1-one)iron and tricarbonyl(η-N-methoxycarbonyl-1H-azepine)-iron and -ruthenium. A 1,6 adduct is also obtained with the azepineiron system. Deuteriation experiments show that the unco-ordinated double bond is the initial site of electrophilic attack. The 1,3-tetracyanoethylene adduct of the cycloheptatrienoneiron complex readily isomerises to a 1,5 adduct in solution. The generally accepted dipolar mechanism for these cycloaddition reactions is critically assessed and an alternative concerted reaction path is presented.",
author = "Michael Green and Heathcock, {Susan M.} and Turney, {Terence W.} and Mingos, {D. Michael P.}",
year = "1977",
month = "12",
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language = "English",
pages = "204--211",
journal = "Journal of the Chemical Society. Dalton Transactions",
issn = "1477-9226",
publisher = "The Royal Society of Chemistry",
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TY - JOUR

T1 - Reactions of co-ordinated ligands. Part 15. The cycloaddition of electronegatively substituted unsaturated systems to tricarbonyl(η-N-methoxycarbonyl-1H-azepine)-iron and -ruthenium and tricarbonyl(η-cyclohepta-2,4,6-trien-1-one)iron

AU - Green, Michael

AU - Heathcock, Susan M.

AU - Turney, Terence W.

AU - Mingos, D. Michael P.

PY - 1977/12/1

Y1 - 1977/12/1

N2 - Hexafluoroacetone, tetracyanoethylene, and 1,1 dicyano-2,2-bis(trifluoromethyl)ethyiene form exo-1,3 adducts with tricarbonyl(η-cyclohepta-2,4,6-trien-1-one)iron and tricarbonyl(η-N-methoxycarbonyl-1H-azepine)-iron and -ruthenium. A 1,6 adduct is also obtained with the azepineiron system. Deuteriation experiments show that the unco-ordinated double bond is the initial site of electrophilic attack. The 1,3-tetracyanoethylene adduct of the cycloheptatrienoneiron complex readily isomerises to a 1,5 adduct in solution. The generally accepted dipolar mechanism for these cycloaddition reactions is critically assessed and an alternative concerted reaction path is presented.

AB - Hexafluoroacetone, tetracyanoethylene, and 1,1 dicyano-2,2-bis(trifluoromethyl)ethyiene form exo-1,3 adducts with tricarbonyl(η-cyclohepta-2,4,6-trien-1-one)iron and tricarbonyl(η-N-methoxycarbonyl-1H-azepine)-iron and -ruthenium. A 1,6 adduct is also obtained with the azepineiron system. Deuteriation experiments show that the unco-ordinated double bond is the initial site of electrophilic attack. The 1,3-tetracyanoethylene adduct of the cycloheptatrienoneiron complex readily isomerises to a 1,5 adduct in solution. The generally accepted dipolar mechanism for these cycloaddition reactions is critically assessed and an alternative concerted reaction path is presented.

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U2 - 10.1039/DT9770000204

DO - 10.1039/DT9770000204

M3 - Article

SP - 204

EP - 211

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

SN - 1477-9226

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