Tris-Silanide f-Block Complexes: Insights into Paramagnetic Influence on NMR Chemical Shifts

Benjamin Reant, Fraser J. Mackintosh, Gemma Gransbury, Carlo Andrea Mattei, Barak Alnami, Benjamin Atkinson, Katherine L. Bonham, Jack Baldwin, Ashley Wooles, Inigo Vitorica-Yrezabal, Daniel Lee, Nicholas Chilton, Stephen Liddle, David Mills

Research output: Contribution to journalArticlepeer-review

Abstract

The paramagnetism of f-block ions has been exploited in chiral shift reagents and magnetic resonance imaging, but these applications tend to focus on 1H NMR shifts as paramagnetic broadening makes less sensitive nuclei more difficult to study. Here we report a solution and solid-state (ss) 29Si NMR study of an isostructural series of locally D3h-symmetric early f-block metal(III) tris-hypersilanide complexes, [M{Si(SiMe3)3}3(THF)2] (1-M; M = La, Ce, Pr, Nd, U); 1-M were also characterized by single crystal and powder X-ray diffraction, EPR, ATR-IR and UV-Vis-NIR spectroscopies, SQUID magnetometry and elemental analysis. Only one SiMe3 signal was observed in the 29Si ssNMR spectra of 1-M, whilst two SiMe3 signals were seen in solution 29Si NMR spectra of 1-La and 1-Ce. This is attributed to dynamic averaging of the SiMe3 groups in 1-M in the solid state due to free rotation of the M–Si bonds, and dissociation of THF from 1-M in solution to give the locally C3v-symmetric complexes [M{Si(SiMe3)3}3(THF)n] (n = 0 or 1), which show restricted rotation of M–Si bonds on the NMR timescale. Density functional theory and complete active space self-consistent field spin-orbit calculations were performed on 1-M and desolvated solution species to model paramagnetic NMR shifts. We find excellent agreement of experimental 29Si NMR data for diamagnetic 1-La, suggesting n = 1 in solution, and reasonable agreement of calculated paramagnetic shifts of SiMe3 groups for 1-M (M = Pr and Nd); the NMR shifts for metal-bound 29Si nuclei could only be reproduced for diamagnetic 1-La, showing the current limitations of pNMR calculations for larger nuclei.
Original languageEnglish
JournalJACS Au
Publication statusAccepted/In press - 26 Jun 2024

Keywords

  • Lanthanide
  • Actinide
  • Paramagnetic
  • NMR spectroscopy
  • Magic Angle Spinning
  • ab initio
  • DFT calculation

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