Synthetic Utility of [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>Ln][(μ-Ph)<sub>2</sub>BPh<sub>2</sub>] in Accessing [(C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>LnR]<i><sub>x</sub></i> Unsolvated Alkyl Lanthanide Metallocenes, Complexes with High C−H Activation Reactivity
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The loosely ligated [BPh4]1- ion in [(C5Me5)2Ln][(μ-Ph)2BPh2] can be readily displaced by alkyllithium or potassium reagents to provide access to unsolvated alkyl lanthanide metallocenes, [(C5Me5)2LnR]x, which display high C−H activation reactivity. [(C5Me5)2SmMe]3, [(C5Me5)2LuMe]2, [(C5Me5)2LaMe]x, (C5Me5)2Sm(CH2Ph), [(C5Me5)2Sm(CH2SiMe3)]x, and [(C5Me5)2SmPh]2 were prepared in this way. [(C5Me5)2SmMe]3 metalates toluene, benzene, SiMe4, and (C5Me5)1- ligands to make (C5Me5)2Sm(CH2Ph), [(C5Me5)2SmPh]2, [(C5Me5)2Sm(CH2SiMe3)]x, and (C5Me5)6Sm4[C5Me3(CH2)2]2, respectively. These C−H activation reactions can be done using an in situ synthesis of [(C5Me5)2LnMe]x such that the [(C5Me5)2Ln][(μ-Ph)2BPh2]/LiMe/RH combination provides a facile route to a variety of unsolvated [(C5Me5)2LnR]x products.
