Dynamic Conformational Behavior in Stable Pentaorganosilicates

Leon J.P. van der Boon, Jesper H. Hendriks, Danny Roolvink, Sean J. O'Kennedy, Martin Lutz, J. Chris Slootweg, Andreas W. Ehlers*, Koop Lammertsma

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review


Silicates with five organic groups are conformationally dynamic even with two bidentate ligands. Symmetry breaking by incorporating a single nitrogen or phosphorus atom provides insight into their dynamic behavior. N-containing silicates with bidentate 2-phenylpyridine, biphenyl, and a Me (8), Et (9) or Ph (10) ligand were studied comprehensively by NMR spectroscopy and DFT theory to reveal two isoenergetic conformers with a barrier of ca. 10 kcal mol–1. P-containing silicate 14 with bidentate triphenylphosphane, biphenyl, and Me ligands is subject to multiple Berry pseudorotations, turnstile rotations, and conformational flexibility of the P-center. The stability increased by masking the P-center with a BH3 group (16). DFT and NMR modeling reveal two isoenergetic conformers for 16 with a barrier of ca. 19 kcal‧mol–1 for a complex interconversion pathway. This barrier bodes well for the design of configurationally stable chiral-at-metal transition metal catalysts.

Original languageEnglish
Pages (from-to)3318-3328
Number of pages11
JournalEuropean Journal of Inorganic Chemistry
Issue number28
Early online date7 Jul 2019
Publication statusPublished - 31 Jul 2019


  • Berry pseudorotation
  • Density functional calculations
  • Hypervalent compounds
  • Silicates
  • Silicon


Dive into the research topics of 'Dynamic Conformational Behavior in Stable Pentaorganosilicates'. Together they form a unique fingerprint.

Cite this