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Mechanism of Hydride Abstraction by Cyclopentadienone‐Ligated Carbonylmetal Complexes (M = Ru, Fe)
Author(s) -
Thorson Megan K.,
Klinkel Kortney L.,
Wang Jianmei,
Williams Travis J.
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200800975
Subject(s) - chemistry , hydride , ruthenium , electrophile , catalysis , photochemistry , reaction mechanism , ligand (biochemistry) , transfer hydrogenation , medicinal chemistry , organic chemistry , hydrogen , biochemistry , receptor
Cyclopentadienone‐ligated ruthenium complexes, such as Shvo's catalyst, are known to oxidize reversibly alcohols to the corresponding carbonyl compounds. The mechanism of this reaction has been the subject of some controversy, but it is generally believed to proceed through concerted transfer of proton and hydride, respectively, to the cyclopentadienone ligand and the ruthenium center. In this paper we further study the hydride transfer process as an example of a coordinatively directed hydride abstraction by adding quantitative understanding to some features of this mechanism that are not well understood. We find that an oxidant as weak as acetone can be used to re‐oxidize the intermediate ruthenium hydride without catalyst re‐oxidation becoming rate‐limiting. Furthermore, C–H cleavage is a significantly electrophilic event, as demonstrated by a Hammett reaction parameter of ρ = –0.89. We then describe how the application of our mechanistic insights obtained from the study have enabled us to extend the ligand‐directed hydride abstraction strategy to include a rare example of an iron(0) oxidation catalyst.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)