Kinetic Deuterium Isotope Effects on Ligand Migrations in Metal Hydrides. 21

Julia Bracker-Novak, Sharad Hajela, Michael Lord, Minsheng Zhang, Edward Rosenberg, Roberto Gobetto, Luciano Milone, Domenico Osella

Risultato della ricerca: Contributo su rivistaArticolo in rivistapeer review

Abstract

Variable-temperature (VT)1H and13C NMR studies of the complexes (µ-X)2OS3(CO)932-(CH3CH2)2C2) (X = H or D) reveal that alkyne migration over the face of the cluster is directly linked to hydride migrations on the metal core as evidenced by a temperature-independent isotope effect (kHH/kDD = 1.7). In a related study of the VT13C NMR of (µ-x)2M3(CO)93-S) (X = H or D; M = Ru, Os) the observation of a kHH/kDD = 1.6 for both the osmium and ruthenium complexes demonstrates that the first stage of carbonyl averaging is brought about by hydride migration and not axial‒radial exchange of carbonyl groups, a process that occurs only at higher temperatures. The mechanistic implications of these results are discussed in the context of the reactivity of metal clusters and the dynamic properties of the metal‒hydrogen bond.

Lingua originaleInglese
pagine (da-a)1379-1382
Numero di pagine4
RivistaOrganometallics
Volume9
Numero di pubblicazione5
DOI
Stato di pubblicazionePubblicato - 1990
Pubblicato esternamente

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