Non-Cyclopentadienyl Coordination Environment;Synthesis,Structure and Catalytic Activity in Olefin PolymerizationNon-Cyclopentadienyl Coordination Environment;Synthesis,Structure and Catalytic Activity in Olefin Polymerization

摘要

The reaction of anhydrous LuCl_3 with a twofold molar excess of lithium guanidinate [Li((Me_3Si)_2NC(Ni'Pr)_2}],obtained in situ from the amide [LiN(SiMe_3)_2(Et_2O)] and 1,3-diisopropyl-carbodiimide in THF,yields the bis (guanidinate) "ate" complex [Lu)(Me_3Si)_2NC(NiPr)_2}_2(mu-Cl)_2Li(THF)_2] (1).The alkyl-lutetium derivative [Lu|(Me_3Si)_2NC(NiPr)_2}_2(CH_2SiMe_3)] (2) was synthesized by a metathesis reaction of 1 with LiCH_2.SiMe_3 in toluene.The treatment of 2 with an equimolar amount of PhSiH_3 in hexane at room temperature results in the first known dimeric lanthanide hydride in a bis(guanidi-nate) coordination environment,[Lu((Me_3Si)_2NC(NiPr)_2}_2(mu-H)]_2 (3).The crystal structures of complexes 1 and 3 have been determined by X-ray crystallography.The hydrido complex 3 was found to catalyze polymerization of ethylene,pro-pylene and styrene.