Synthetic Utility of [(C_5Me_5)_2Ln][(mu-Ph)_2BPh_2] in Accessing [(C_5Me_5)_2LnR]_x Unsolvated Alkyl Lanthanide Metallocenes,Complexes with High C-H Activation Reactivity

摘要

loosely ligated [BPh_4]~(1-) ion in [(C_5Me_5)_2Ln][(mu-Ph)_2BPh_2] can be readily displaced by alkyllithium or potassium reagents to provide access to unsolvated alkyl lanthanide metallocenes,[(C_5-Me_5)_2LnR]_x,which display high C-H activation reactivity.[(C_5Me_5)_2SmMe]_3,[(C_5Me_5)_2LuMe]_2,[(C_5Me_5)_2-LaMe]_x,(C_5Me_5)_2Sm(CH_2Ph),[(C_5Me_5)_2Sm(CH_2SiMe_3)]_x,and [(C_5Me_5)2SmPh]_2 were prepared in this way.[(C_5Me_5SmMe]_s metalates toluene,benzene,SiMe_4,and (C_5Me_5)~(1-) ligands to make (C_5Me_5)_2Sm(CH_2-Ph),[(C_5Me_5)_2SmPh]_2,[(C_5Me_5)_2Sm(CH_2SiMe_3)]_x,and (C_5Me_5)_6Sm_4[C_5Me_3(CH_2)_2]_2,respectively.These C-H activation reactions can be done using an in situ synthesis of [(C_5Me_5)_2LnMe]_x such that the [(C_5Me_5)_2Ln]-[(mu-Ph)_2BPh_2]/LiMe/RH combination provides a facile route to a variety of unsolvated [(C_5Me_5)_2LnR]_x products.