Rare‐Earth Metal Alkyl and Hydride Complexes Supported by a Linked Anilido–cyclopentadienyl Ligand: Synthesis, Structure, and Reactivity

Trimethylsilylmethyl complexes of the type [Ln(η 5 ‐C 5 Me 4 CH 2 SiMe 2 NC 6 H 4 R‐4‐κN)(CH 2 SiMe 3 )(thf) n ] containing a dianionic ligand [C 5 Me 4 CH 2 SiMe 2 NC 6 H 4 R‐4] 2– with a para ‐substituted anilido group and a CH 2 SiMe 2 link were prepared. The yttrium complex [Y(η 5 ‐C 5 Me 4 CH 2 SiMe 2 NPh‐κN)(CH 2 SiMe 3 )(thf) 2 ] ( 2a ) reacts with H 2 to generate the corresponding dimeric hydride [Y(η 5 ‐C 5 Me 4 CH 2 SiMe 2 NPh‐κN)(μ‐H)(thf)] 2 ( 5a ). Pyridine inserts into the Y–H bond in a 1,2‐fashion to afford the stable 2‐hydropyridyl complex [Y(η 5 ‐C 5 Me 4 CH 2 SiMe 2 NPh‐κN)(η 1 ‐NC 5 H 6 )(py) 2 ] ( 6a ). Upon reaction with t BuC≡CH, protonolysis takes place to give the dimeric alkynyl complex [Y(η 5 ‐C 5 Me 4 CH 2 SiMe 2 NPh‐κN)(μ‐C≡C t Bu)(thf)] 2 ( 7a ).(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)