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Direct observation of. eta. sup 2 -arene complexes of ((C sub 5 Me sub 5 )Rh(PMe sub 3 ))

Journal Article · · Journal of the American Chemical Society; (United States)
DOI:https://doi.org/10.1021/ja00205a025· OSTI ID:7039040
;  [1]
  1. Univ. of Rochester, NY (United States)
Over the past few years, there has been substantial progress in studies of the mechanism of activation of aliphatic aromatic C-H bonds by transition metals. In particular, earlier studies in the authors group have indicated that arenes coordinate to ((Ce{sub 5}Me{sub 5})Rh(PMe{sub 3})) in an {eta}{sup 2} fashion prior to C-H bond oxidative addition, and that this initial coordination permits the activation of aromatic C-H bonds to compete with aliphatic C-H bond activation. The evidence for {eta}{sup 2}-arene coordination relies heavily on indirect experiments (intramolecular isomerization of an aryl deuteride, kinetic isotope effect experiments), as the only direct evidence for arene coordination was with p-di-tert-butylbenzene at low temperature. They report here the room temperature observation of {eta}{sup 2}-arene complexes of ((C{sub 5}Me{sub 5})Rh(PMe{sub 3})) and an equilibrium between and {eta}{sup 2}-arene complex and its aryl hydride counterpart.
DOE Contract Number:
FG02-86ER13569
OSTI ID:
7039040
Journal Information:
Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 111; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English