New analogues of Cp′ 3 Ln (Cp′ = C 5 H 4 SiMe 3 , Ln = rare earth) complexes have been synthesized with the largest and smallest lanthanides, La and Lu. Due to the smaller size of Lu, the reaction of LuCl 3 with 3 equiv of KCp′ produced only traces of Cp′ 3 Lu, yielding [Cp′ 2 Lu(μ-Cl)] 2 as the major product. An alternative route was developed in which [Cp′ 2 Lu(μ-Cl)] 2 reacts with (C 3 H 5 )MgCl to form the tetrameric allyl complex [Cp′ 2 Lu(μ-η 1 :η 1 -C 3 H 5 )] 4 . The allyl complex reacts with [HNEt 3 ][BPh 4 ] to generate [Cp′ 2 Lu(THF) 2 ][BPh 4 ], which reacts with KCp′ to produce Cp′ 3 Lu in good yield. The reaction of LaCl 3 with 3 equiv of KCp′ in Et 2 O gave the unsolvated Cp′ 3 La, while the same reaction in rigorously dry THF gave solvated Cp′ 3 La(THF). The reaction of LaCl 3 and KCp′ in improperly dried THF gave the mixed-ligand complex Cp′ 2 CpLa(THF) (Cp = C 5 H 5 ), rather than the expected hydrolysis product, [Cp′ 2 La(μ-OH)] 2 .

The first crystallographic characterization of bismuth complexes containing benzyl ligands is reported. The NCN pincer ligand complex, Ar′BiCl 2 [Ar′ = 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 ], reacts with (PhCH 2 )MgCl to form Ar′Bi(η 1 -CH 2 Ph) 2 in high yield. X-ray crystallography and spectroscopic studies confirm η 1 -bonding of the benzyl ligands in Ar′Bi(η 1 -CH 2 Ph) 2 as well as in the homoleptic Bi(η 1 -CH 2 Ph) 3 .