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January 24, 2010 | History

Photolytic reactivity of [1]- and [2]metallocenophanes 1 edition

Photolytic reactivity of [1]- and [2]metallocenophanes
David E. Herbert

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Photolytic reactivity of [1]- and [2]metallocenophanes.

Published 2006 .
Written in English.

About the Book

The enhanced reactivity of [Fe(eta-C5H4CH 2)2] with ultraviolet irradiation allows for stoichiometric ring-opening by alkyl Cp anions [C5H4R]- (R = Me, tBu) via attack at an Fe-Cp bond. The reactivity of the photo-excited monomer towards various initiators has been examined. Short, linear, partially-soluble oligomers of the type [fcCH 2CH2]x (x = 3, 4) were prepared.Reversible, haptotropic shifts of cyclopentadienyl (Cp) ligands in moderately strained [1]- and [2]metallocenophanes [Fe(eta-C5H 4)2SiMe2] and [Fe(eta-C5H4CH 2)2] have been studied. These complexes, stable as ansa metallocenes in solution, appear to form ring-slipped species on UV photo-irradiation in strong donor solvents.Similar but irreversible haptotropic shifts of cyclopentadienyl ligands in highly strained [2]metallocenophanes [Ru(eta-C5H4CH 2)2] and [Ru(eta-C5H4(CMe)2 )2] have been shown to proceed without photo-initiation.The presence of monodentate or chelating phosphines allowed for the isolation of novel eta1-Cp ring-slipped complexes. At elevated temperatures, these products retroconvert to reform the ansa metallocene, freeing the coordinated phosphine.

Edition Notes

Advisor: Ian Manners.

Source: Masters Abstracts International, Volume: 44-06, page: 2808.

Thesis (M.Sc.)--University of Toronto, 2006.

Electronic version licensed for access by U. of T. users.

ROBARTS MICROTEXT copy on microfiche.

The Physical Object

Pagination
58 leaves.
Number of pages
58

ID Numbers

Open Library
OL19215544M
ISBN 13
9780494163184

History Created December 11, 2009 · 2 revisions Download catalog record: RDF / JSON

January 24, 2010 Edited by WorkBot add more information to works
December 11, 2009 Created by WorkBot add works page