Organolutetium vinyl and tuck-over complexes via C-H bond activation |
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Authors: | Evans William J Champagne Timothy M Ziller Joseph W |
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Affiliation: | Department of Chemistry, University of California, Irvine, California 92697-2025, USA. wevans@uci.edu |
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Abstract: | The vinyl C-H bond of tetramethylfulvene is activated in the presence of [(C5Me5)2LuH]x, 1, to form a vinyl organolutetium complex, (C5Me5)2Lu(CH=C5Me4), 2. Also formed in the reaction is the "tuck-over" complex, (C5Me5)2Lu(mu-H)(mu-eta1:eta5-CH2C5Me4)Lu(C5Me5), 3, containing a (CH2C5Me4)2- moiety long postulated to exist in organolutetium chemistry but never crystallographically characterized. Evidence for these C-H bond activations by a "(C5Me5)3Lu" intermediate, 4, is presented. Complex 3 can also be made in high yield by thermolysis of 1. Under H2, 1 catalytically hydrogenates TMF to C5Me5H. |
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