Synthetic utility of [(C5Me5)2Ln][(mu-Ph)2BPh] in accessing [(C5Me5)2LnR]x unsolvated alkyl lanthanide metallocenes, complexes with high C-H activation reactivity |
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| Authors: | Evans William J Perotti Jeremy M Ziller Joseph W |
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| Institution: | Department of Chemistry, University of California, Irvine, California 92697-2025, USA. wevans@uci.edu |
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| Abstract: | The loosely ligated BPh4]1- ion in (C5Me5)2Ln](mu-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)6Sm4C5Me3(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](mu-Ph)2BPh2]/LiMe/RH combination provides a facile route to a variety of unsolvated (C5Me5)2LnR]x products. |
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