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

✍ Scribed by Alexander A. Trifonov; Elena A. Fedorova; Georgy K. Fukin; Mikhail N. Bochkarev

• Book ID: 102170765
• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: English
• Weight: 136 KB
• Volume: 2004
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200400425

✦ Synopsis

Abstract

The reaction of anhydrous LuCl~3~ with a twofold molar excess of lithium guanidinate [Li{(Me~3~Si)~2~NC(N__i__Pr)~2~}], obtained in situ from the amide [LiN(SiMe~3~)~2~(Et~2~O)] and 1,3‐diisopropylcarbodiimide in THF, yields the bis(guanidinate) “ate” complex [Lu{(Me~3~Si)~2~NC(N__i__Pr)~2~}~2~(μ‐Cl)~2~Li(THF)~2~] (1). The alkyllutetium derivative [Lu{(Me~3~Si)~2~NC(N__i__Pr)~2~}~2~(CH~2~SiMe~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(guanidinate) coordination environment, [Lu{(Me~3~Si)~2~NC(N__i__Pr)~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)