Post‐Metallocene Hydridolanthanide Chemistry: [Lu{(Me3Si)2NC(NiPr)2}2(μ‐H)]2 — A Novel Lanthanide Hydride in a Non‐Cyclopentadienyl Coordination Environment; Synthesis, Structure and Catalytic Activity in Olefin Polymerization

The reaction of anhydrous LuCl3 with a twofold molar excess of lithium guanidinate [Li{(Me3Si)2NC(NiPr)2}], obtained in situ from the amide [LiN(SiMe3)2(Et2O)] and 1,3‐diisopropylcarbodiimide in THF, yields the bis(guanidinate) “ate” complex [Lu{(Me3Si)2NC(NiPr)2}2(μ‐Cl)2Li(THF)2] (1). The alkyllutetium derivative [Lu{(Me3Si)2NC(NiPr)2}2(CH2SiMe3)] (2) was synthesized by a metathesis reaction of 1 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)2NC(NiPr)2}2(μ‐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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)