Organolutetium Vinyl and Tuck-Over Complexes via C−H Bond Activation

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(μ-H)(μ-η:η5-CH2C5Me4)Lu(C5Me5), 3, containing a (CH2C5Me4)- 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.