New early-late heterobimetallic hydrides (L2ZrCl)(Cp*Ir)(μ-H)3 (1;
L ) Cp derivative, Cp* ) η5-C5Me5) were synthesized from
zirconocene derivatives (L2ZrCl2) and LiCp*IrH3 via a salt elimination
reaction and structurally characterized by NMR and X-ray analyses.
Upon treatment of 1 with an alkyllithium reagent, hydride abstraction
complex 4 underwent thermolytic ligand elimination at the Zr-Ir
system to yield a novel planar square complex (L2Zr)2(Cp*Ir)2(μ3-
H)4 (2). When a labeling study of the reaction was conducted, it
was found that the conversion of 1 to 2 involves rapid aromatic
and benzylic C-H activation by a coordinatively unsaturated
dinuclear complex (L2Zr)(Cp*Ir)(H)2 (3).
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