Synthesis and characterization of (mono)pentamethylcyclopentadienyl lutetium complexes: Formation of bipyridyl-stabilized alkyls, anilides, and terminal acetylides

The alkyl complex [Lu(CH2SiMe3)(3)(THF)(2)] reacts with pentamethylcyclopentadiene (Cp*H), giving [CP*Lu(CH2SiMe3)(2)(THF)] (1). Complex 1 reacts with 1,2-dimethoxyethane (DME), affording [Cp*Lu(CH2SiMe3)(2)(DME)] (2). Complex 1 also reacts with 2,2'-bipyridine (bipy) to give [Cp*Lu(CH2SiMe3)(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)(CH2SiMe3)(bipy)] (4) (Ar = 2,6-Pri(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)(mu-eta(2) : eta(2)-PhC4Ph)] . 2(C6H6) (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.