Post-metallocene hydridolanthanide chemistry: [Lu{(Me3Si)(2)NC(NiPr)(2)}(2)(mu-H)](2) - A novel lanthanide hydride in a non-cyclopentadienyl coordination environment; Synthesis, structure and catalytic activity in olefin polymerization

摘要

The reaction of anhydrous LuCl3 with a twofold molar excess of lithium guanidinate [Li{(Me3Si)(2)NC(NiPr)(2)}], obtained in situ from the amide [LiN(SiMe3)(2)(Et2O)] and 1,3-diisopropyl-carbodiimide in THF, yields the bis(guanidinate) "ate" complex [Lu{(Me3Si)(2)NC(NiPr)(2)}(2)(mu-Cl)(2)Li(THF)(2)] (1). The alkyllutetium derivative [Lu{(Me3Si)(2)NC(NiPr)(2)}(2)(CH2SiMe3)] (2) was synthesized by a metathesis reaction of I with LiCH2SiMe3 in toluene. The treatment of 2 with an equimolar amount of PhSiH3 in hexane at room temperature results in the first known dimeric lanthanide hydride in a bis(guanidinate) coordination environment, [Lu{(Me3Si)(2)NC(NiPr)(2)}(2)(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, propylene and styrene. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).