Physicochemical Properties of Near-Linear Lanthanide(II) Bis(silylamide) Complexes (Ln = Sm, Eu, Tm, Yb)

High Resolution Image Download MS PowerPoint Slide Following our report of the first near-linear lanthanide (Ln) complex, [Sm(N †† ) 2 ] ( 1 ), herein we present the synthesis of [Ln(N †† ) 2 ] [N †† = {N(Si i Pr 3 ) 2 }; Ln = Eu ( 2 ), Tm ( 3 ), Yb ( 4 )], thus achieving approximate uniaxial geometries for a series of “traditional” Ln II ions. Experimental evidence, together with calculations performed on a model of 4, indicates that dispersion forces are important for stabilization of the near-linear geometries of 1 – 4 . The isolation of 3 under a dinitrogen atmosphere is noteworthy, given that “[Tm(N″)(μ-N″)] 2 ” (N″ = {N(SiMe 3 ) 2 }) has not previously been structurally authenticated and reacts rapidly with N 2 (g) to give [{Tm(N″) 2 } 2 (μ-η 2:η 2 -N 2 )]. Complexes 1 – 4 have been characterized as appropriate by single-crystal X-ray diffraction, magnetic measurements, electrochemistry, multinuclear NMR, electron paramagnetic resonance (EPR), and electronic spectroscopy, along with computational methods for 3 and 4 . The remarkable geometries of monomeric 1 – 4 lead to interesting physical properties, which complement and contrast with comparatively well understood dimeric [Ln(N″)(μ-N″)] 2 complexes. EPR spectroscopy of 3 shows that the near-linear geometry stabilizes m J states with oblate spheroid electron density distributions, validating our previous suggestions. Cyclic voltammetry experiments carried out on 1 – 4 did not yield Ln II reduction potentials, so a reactivity study of 1 was performed with selected substrates in order to benchmark the Sm III → Sm II couple. The separate reactions of 1 with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), azobenzene, and benzophenone gave crystals of [Sm(N †† ) 2 (TEMPO)] ( 5 ), [Sm(N †† ) 2 (N 2 Ph 2 )] ( 6 ), and [Sm(N †† ){μ-OPhC(C 6 H 5 )CPh 2 O-κ O, O ′}] 2 ( 7 ), respectively. The isolation of 5 – 7 shows that the Sm II center in 1 is still accessible despite having two bulky N †† moieties and that the N-donor atoms are able to deviate further from linearity or ligand scrambling occurs in order to accommodate another ligand in the Sm III coordination spheres of the products.