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

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

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
Volume2019
Issue number28
Early online date7 Jul 2019
DOIs
Publication statusPublished - 31 Jul 2019

Fingerprint

Silicates
Ligands
Discrete Fourier transforms
Phosphorus
Nuclear magnetic resonance spectroscopy
Transition metals
Nitrogen
Nuclear magnetic resonance
Atoms
Catalysts
diphenyl

Keywords

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

Cite this

van der Boon, Leon J.P. ; Hendriks, Jesper H. ; Roolvink, Danny ; O'Kennedy, Sean J. ; Lutz, Martin ; Slootweg, J. Chris ; Ehlers, Andreas W. ; Lammertsma, Koop. / Dynamic Conformational Behavior in Stable Pentaorganosilicates. In: European Journal of Inorganic Chemistry. 2019 ; Vol. 2019, No. 28. pp. 3318-3328.
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van der Boon, LJP, Hendriks, JH, Roolvink, D, O'Kennedy, SJ, Lutz, M, Slootweg, JC, Ehlers, AW & Lammertsma, K 2019, 'Dynamic Conformational Behavior in Stable Pentaorganosilicates' European Journal of Inorganic Chemistry, vol. 2019, no. 28, pp. 3318-3328. https://doi.org/10.1002/ejic.201900641

Dynamic Conformational Behavior in Stable Pentaorganosilicates. / van der Boon, Leon J.P.; Hendriks, Jesper H.; Roolvink, Danny; O'Kennedy, Sean J.; Lutz, Martin; Slootweg, J. Chris; Ehlers, Andreas W.; Lammertsma, Koop.

In: European Journal of Inorganic Chemistry, Vol. 2019, No. 28, 31.07.2019, p. 3318-3328.

Research output: Contribution to JournalArticleAcademicpeer-review

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van der Boon LJP, Hendriks JH, Roolvink D, O'Kennedy SJ, Lutz M, Slootweg JC et al. Dynamic Conformational Behavior in Stable Pentaorganosilicates. European Journal of Inorganic Chemistry. 2019 Jul 31;2019(28):3318-3328. https://doi.org/10.1002/ejic.201900641