Synthesis and Characterization of (Mono)pentamethylcyclopentadienyl Lutetium Complexes: Formation of Bipyridyl-Stabilized Alkyls, Anilides, and Terminal Acetylides

The alkyl complex [Lu(CH 2 SiMe 3 ) 3 (THF) 2 ] reacts with pentamethylcyclopentadiene (Cp*H), giving [Cp*Lu(CH 2 SiMe 3 ) 2 (THF)] ( 1 ). Complex 1 reacts with 1,2-dimethoxyethane (DME), affording [Cp*Lu(CH 2 SiMe 3 ) 2 (DME)] ( 2 ). Complex 1 also reacts with 2,2‘-bipyridine (bipy) to give [Cp*Lu(CH 2 SiMe 3 ) 2 (bipy)] ( 3 ). The dialkyl complex 3 reacts with 1.0 equiv of 2,6-diisopropylaniline to give the mixed alkyl-anilide [Cp*Lu(NHAr)(CH 2 SiMe 3 )(bipy)] ( 4 ) (Ar = 2,6-Pr i 2 C 6 H 3 ) and the bis(anilide) [Cp*Lu(NHAr) 2 (bipy)] ( 5 ) in a 1.0:0.09 ratio. Complex 5 can be independently synthesized in high yield by treatment of 3 with 2.0 equiv of 2,6-diisopropylaniline or 4 with 1.0 equiv of 2,6-diisopropylaniline. Complex 3 also reacts with 2.0 equiv of phenylacetylene to afford dimeric [{Cp*Lu(CCPh)(bipy)} 2 (μ-η 2:η 2 -PhC 4 Ph)]·2(C 6 H 6 ) ( 6 ). Complex 6 reacts with THF and pyridine (py), giving terminal (bis)acetylide complexes [Cp*Lu(CCPh) 2 (bipy)(THF)] ( 7 ) and [Cp*Lu(CCPh) 2 (bipy)(py)] ( 8 ), respectively. The solid-state structures of 1, 2, 4, 5, 6, and 8 are reported.