Homoleptic Trivalent Tris(alkyl) Rare Earth Compounds

Abstract

Homoleptic tris(alkyl) rare earth complexes Ln{C(SiHMe₂)₃}₃ (Ln = La, 1a; Ce, 1b; Pr, 1c; Nd, 1d) are synthesized in high yield from LnI₃THF_n and 3 equiv of KC(SiHMe₂)₃. X-ray diffraction studies reveal 1a-d are isostructural, pseudo-C₃-symmetric molecules that contain two secondary Ln↼HSi interactions per alkyl ligand (six total). Spectroscopic assignments are supported by comparison with Ln{C(SiDMe₂)₃}₃ and DFT calculations. The Ln↼HSi and terminal SiH exchange rapidly on the NMR time scale at room temperature, but the two motifs are resolved at low temperature. Variable-temperature NMR studies provide activation parameters for the exchange process in 1a (ΔH^⧧ = 8.2(4) kcal·mol^-1; ΔS^⧧ = -1(2) cal·mol^-1K^-1) and 1a-d₉ (ΔH^⧧ = 7.7(3) kcal·mol^-1; ΔS^⧧ = -4(2) cal·mol^-1K^-1). Comparisons of lineshapes, rate constants (k_H/k_D), and slopes of ln(k/T) vs 1/T plots for 1a and 1a-d₉ reveal that an inverse isotope effect dominates at low temperature. DFT calculations identify four low-energy intermediates containing five β-Si-H⇀Ln and one γ-C-H⇀Ln. The calculations also suggest the pathway for Ln↼HSi/SiH exchange involves rotation of a single C(SiHMe₂)₃ ligand that is coordinated to the Ln center through the Ln-C bond and one secondary interaction. These robust organometallic compounds persist in solution and in the solid state up to 80 °C, providing potential for their use in a range of synthetic applications. For example, reactions of Ln{C(SiHMe₂)₃}₃ and ancillary proligands, such as bis-1,1-(4,4-dimethyl-2-oxazolinyl)ethane (HMeC(Ox^Me2)₂) give {MeC(Ox^Me2)₂}Ln{C(SiHMe₂)₃}₂, and reactions with disilazanes provide solvent-free lanthanoid tris(disilazides).