Displacement, reduction, and ligand redistribution reactivity of the cationic mono-C 5Me 5 Ln 2+ complexes (C 5Me 5)Ln(BPh 4) (Ln = Sm, Yb)

Abstract

The reactivity of the mono(pentamethylcyclopentadienyl) divalent lanthanide tetraphenylborate complexes, (C 5Me 5)Ln(BPh 4) (Ln = Sm, 1; Yb, 2), was investigated to determine how Ln 2+ and (BPh 4) 1− reactivity would combine in these species. The (BPh 4) 1− ligand in (C 5Me 5)Yb(BPh 4) can be displaced with KN(SiMe 3) 2 to form the heteroleptic divalent dimer, {(C 5Me 5)Yb[μ-N(SiMe 3) 2]} 2 ( 3). Both 1 and 2 reduce phenazine to give the bis(pentamethylcyclopentadienyl) ligand redistribution products, [(C 5Me 5) 2Ln] 2(μ-C 12H 8N 2). 2,2-Bipyridine is reduced by 1 to yield the ligand redistribution product, (C 5Me 5) 2Sm(C 10H 8N 2) (4), while 2 does not react with bipyridine. Tert-butyl chloride is reduced by 1 to form the trimetallic pentachloride complex [{(C 5Me 5)(THF)Sm} 3(μ-Cl) 5][BPh 4] ( 6), in a reaction that appears to use the reductive capacity of both Sm 2+ and (BPh 4) 1−.