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A Beneficial Kinetic Effect of an η5-C5Me4H Ligand.

TitleA Beneficial Kinetic Effect of an η5-C5Me4H Ligand.
Publication TypeJournal Article
Year of Publication2010
AuthorsBaillie, RA, Tran, T, Thibault, ME, Legzdins, P
JournalJournal of the American Chemical Society
Volume132
Pagination15160 - 15161
Date Published2010///
ISBN Number0002-7863
Keywordsbenzene carbon hydrogen bond activation cyclopentadienyltungsten allyl neopentyl nitrosyl, crystal mol structure cyclopentadienyltungsten allyl phenyl nitrosyl complex, cyclopentadienyl tungsten allyl neopentyl nitrosyl reaction benzene, tetramethylcyclopentadienyl ligand beneficial kinetic effect tungsten nitrosyl benzene activation
Abstract

C-H activation of benzene at 26° by (η5-C5Me5)W(NO)(CH2CMe3)(η3-CH2CHCHMe) results after 4 h in the prodn. of five new organometallic complexes, only two of which are isomers of the desired (η5-C5Me5)W(NO)(C6H5)(η3-CH2CHCHMe) compd. In contrast, the identical reaction involving the η5-C5Me4H analog affords only the Ph complexes during the first 24 h, thereby facilitating their isolation in good yields. This striking difference in reactivity can be attributed to the lesser steric demands of the η5-C5Me4H ligand that result in its complexes reacting at a significantly slower rate. [on SciFinder(R)]