Theoretical Study of the Reactivity of (π-Allyl)molybdenum Complexes

The reactivity of allyl carbons in (π-allyl)molybdenum complexes has been investigated theoretically. The central carbon of the allyl moiety has been shown to be more reactive than the terminal carbons toward nucleophiles in Cp2Mo(η3-allyl)+ by locating a reactant complex, transition states, and pro...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Organometallics 2003-09, Vol.22 (18), p.3649-3658
Hauptverfasser: Suzuki, Tomohiro, Okada, Goro, Hioki, Yasunori, Fujimoto, Hiroshi
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:The reactivity of allyl carbons in (π-allyl)molybdenum complexes has been investigated theoretically. The central carbon of the allyl moiety has been shown to be more reactive than the terminal carbons toward nucleophiles in Cp2Mo(η3-allyl)+ by locating a reactant complex, transition states, and products with the density functional theoretical calculations. Orbital interactions have been analyzed then by applying a paired interacting orbital scheme to the MO wave function. The local electron-accepting ability of allyl carbons has been evaluated, showing that the acidic hardness of reaction sites is a key to understand the higher reactivity of the central carbon. The regioselectivity observed in nucleophilic attacks to CpMo(η3-allyl)(CO)(NO)+ and some other (π-allyl)molybdenum complexes has also been investigated in terms of the local electron-accepting ability of the reaction sites. The terminal carbons are shown to be more reactive in these cases.
ISSN:0276-7333
1520-6041
DOI:10.1021/om0207459