3 years ago

Homoleptic Trivalent Tris(alkyl) Rare Earth Compounds

Homoleptic Trivalent Tris(alkyl) Rare Earth Compounds
Aaron D. Sadow, Bradley M. Schmidt, Smita Patnaik, Igor I. Slowing, KaKing Yan, Cheolbeom Bae, Arkady Ellern, Aradhana Pindwal
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 LnI3THFn and 3 equiv of KC(SiHMe2)3. X-ray diffraction studies reveal 1ad 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 1aH = 8.2(4) kcal·mol–1; ΔS = −1(2) cal·mol–1K–1) and 1a-d9H = 7.7(3) kcal·mol–1; ΔS = −4(2) cal·mol–1K–1). Comparisons of lineshapes, rate constants (kH/kD), 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(OxMe2)2) give {MeC(OxMe2)2}Ln{C(SiHMe2)3}2, and reactions with disilazanes provide solvent-free lanthanoid tris(disilazides).

Publisher URL: http://dx.doi.org/10.1021/jacs.7b09521

DOI: 10.1021/jacs.7b09521

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.