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Low-temperature sup 31 P NMR studies of metal phosphine clusters

Journal Article · · Inorganic Chemistry; (United States)
DOI:https://doi.org/10.1021/ic00008a008· OSTI ID:5564066

(Au(PPh{sub 3})(AuPPh{sub 3}){sub 7}){sup 2+}, (Pt(H)(PPh{sub 3})(AuPPh{sub 3}){sub 8}){sup 3+} show sharp {sup 31}P NMR resonances in solutions at room temperature although from the solid-state structure different phosphine sites are expected. This is due to fluxionality, the chemical exchange of different phosphorus sites. This process can be slowed by lowering the temperature, and in this slow-exchange regime the different phosphine sites can be assigned by means of {sup 31}P homonuclear shift correlated spectroscopy methods. The tensor surface harmonics model, which is used for the description of the bonding in this type of clusters, offers a rationale for the trends in the observed magnitude of the coupling constants. Deviation of this model is observed for the toroidal clusters, in which the peripheral interactions are shown to be stronger than in the spheroidal clusters. 21 refs., 10 figs., 1 tab.

OSTI ID:
5564066
Journal Information:
Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:8; ISSN 0020-1669; ISSN INOCA
Country of Publication:
United States
Language:
English