Ligand Site Exchange Induced by Intrametallic Rearrangement Processes in H2FeRu3(CO)13-x(PR3)x (x = 1, 2)

Wayne L. Gladfelter, Joseph R. Fox, John A. Smegal, Timothy G. Wood, Gregory L. Geoffroy

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Abstract

The fluxional processes which occur in H2FeRu3(CO)12L (L = PMe2Ph, PMe3) and H2FeRu3(CO)11L2 (L = PMe3, PPh3, P(OMe)3, P(OEt)3) have been studied by a combination of variable-temperature 1H, 31P, and 13C NMR spectroscopy. The fluxional processes are basically the same as those which have been shown to occur in the unsubstituted H2FeRu3(CO)13 cluster and involve bridge-terminal CO exchange localized on Fe, cyclic exchange of the carbonyls about the triangular face of the cluster which possesses the bridging CO's, and rearrangement of the metal framework with a corresponding shift of the hydrides and carbonyls. The intrametallic rearrangement process is of profound importance in these substituted derivatives since it leads to exchange of the substitution sites. For the monosubstituted derivatives, this exchange leads to the facile Cs↔C, isomerization observed, and for the disubstituted derivative it renders the phosphorus donor ligands equivalent on the time scale of the NMR measurements.

Original languageEnglish (US)
Pages (from-to)3223-3229
Number of pages7
JournalInorganic Chemistry
Volume20
Issue number10
DOIs
StatePublished - Oct 1981

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