Carbon—Metal Hydrogen Interchange in Organometal Clusters of Ruthenium and Osmium

David M. Skinner, Edward Rosenberg, Julia Bracker-Novak, Silvio Aime, Domenico Osella, Roberto Gobetto, Luciano Milone

Risultato della ricerca: Contributo su rivistaArticolo in rivistapeer review

Abstract

Facile carbon-metal hydrogen exchange is demonstrated by the scrambling of deuterium into the hydrocarbon ligand from the hydride position of (μ-H)(μ33-CH3CH2C═C═C(H)CH3)Os3(CO)9 (I) at 110 °C in a sample initially 80% enriched in deuterium at the hydride position by 1H NMR techniques. Deuterium was incorporated into the allenic hydrogen position and the methylene hydrogens but not into the methyl groups. The observed scrambling is interpreted in terms of reversible formation of a 46e alkyne complex (μ3-η2-Ch3Ch2C≡Cch2Ch3)Os3(CO)9. The analogous ruthenium complex I' was also deuteriated in the hydride position (76%), and the scrambling of deuterium was observed by 1H NMR during its isomerization to the corresponding allylic isomer (μ-H)(μ3-η3-Ch3Ch2C═C(H)═CCH3)Ru3(CO)9 (II). A scrambling pattern similar to that seen for I is observed. These results are considered in terms of the known differences in the ligand dynamics of the organic ligands in structural types I and I', and a two-step mechanism is proposed for the isomerization of I' to II.

Lingua originaleInglese
pagine (da-a)856-858
Numero di pagine3
RivistaOrganometallics
Volume7
Numero di pubblicazione4
DOI
Stato di pubblicazionePubblicato - apr 1988
Pubblicato esternamente

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