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Allyl Complexes of Tungsten from the Rearrangement of Transient Cyclopropyl Precursors
Author(s) -
Parker Kyle D. J.,
Labat Stéphane,
Sotiropoulos JeanMarc,
Miqueu Karinne,
Pimienta Véronique,
Vendier Laure,
Etienne Michel
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900816
Subject(s) - cyclopropane , chemistry , intramolecular force , tungsten , ring (chemistry) , reactivity (psychology) , medicinal chemistry , kinetic energy , bond cleavage , zirconium , stereochemistry , catalysis , inorganic chemistry , organic chemistry , medicine , physics , alternative medicine , pathology , quantum mechanics
This article explores the contrasting reactivity of cyclopropyl complexes of early transition metals. [Cp*W(NO)(CH 2 R)( c ‐C 3 H 5 )] (R = SiMe 3 , Ph, t ‐Bu) generated in THF solution from [Cp*W(NO)(CH 2 R)Cl] and [Mg( c ‐C 3 H 5 ) 2 (dioxane) x ] readily rearrange to η 3 ‐allyl derivatives [Cp*W(NO)(CH 2 R)(η 3 ‐C 3 H 5 )] by an intramolecular ring opening reaction. Both direct and catalyzed pathways are revealed by kinetic studies. Computational modeling indicates the ring opening reaction is preferred on thermodynamic grounds for tungsten whereas kinetic products arising from β‐H abstraction reactions of cyclopropane are observed for related zirconium and niobium complexes reported previously. The energetic accessibility and the nature of the LUMO in the tungsten complexes promote distal CC bond cleavage in the cyclopropyl ring.