Chiral Control in Pentacoordinate Systems: The Case of Organosilicates

Leon J.P. Van Der Boon, Laurens Van Gelderen, Tim R. De Groot, Martin Lutz, J. Chris Slootweg, Andreas W. Ehlers, Koop Lammertsma

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Chirality at the central element of pentacoordinate systems can be controlled with two identical bidentate ligands. In such cases the topological Levi-Desargues graph for all the Berry pseudorotations (BPR, max. 20) reduces to interconnected inner and outer "circles" that represent the dynamic enantiomer pair. High enough barriers of the BPR crossovers between the two circles is all what is needed to ascertain chiral integrity. This is illustrated computationally and experimentally for the organosilicates 7 and 10 that carry besides a Me (a), Et (b), Ph (c), or F (d) group two bidentate 2-(phenyl)benzo[b]-thiophene or 2-(phenyl)naphthyl ligands, respectively. The enantiomers of tetraorganosilane precursor 9 could be separated by column chromatography. Their chiral integrity persisted on forming the silicates. CD spectra are reported for 10c. Fluoro derivative 10d is shown to have its electronegative F substituent in an equatorial position, is stable toward hydrolysis, and its enantiomers do not racemize at ambient temperatures, while those of 10c racemize slowly.

Original languageEnglish
Pages (from-to)12697-12708
Number of pages12
JournalInorganic Chemistry
Volume57
Issue number20
Early online date2 Oct 2018
DOIs
Publication statusPublished - 15 Oct 2018

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Enantiomers
enantiomers
integrity
Ligands
Silicates
Column chromatography
ligands
Chirality
chromatography
thiophenes
chirality
ambient temperature
hydrolysis
Hydrolysis
silicates
crossovers
Derivatives
Temperature

Cite this

Van Der Boon, L. J. P., Van Gelderen, L., De Groot, T. R., Lutz, M., Slootweg, J. C., Ehlers, A. W., & Lammertsma, K. (2018). Chiral Control in Pentacoordinate Systems: The Case of Organosilicates. Inorganic Chemistry, 57(20), 12697-12708. https://doi.org/10.1021/acs.inorgchem.8b01861
Van Der Boon, Leon J.P. ; Van Gelderen, Laurens ; De Groot, Tim R. ; Lutz, Martin ; Slootweg, J. Chris ; Ehlers, Andreas W. ; Lammertsma, Koop. / Chiral Control in Pentacoordinate Systems : The Case of Organosilicates. In: Inorganic Chemistry. 2018 ; Vol. 57, No. 20. pp. 12697-12708.
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Van Der Boon, LJP, Van Gelderen, L, De Groot, TR, Lutz, M, Slootweg, JC, Ehlers, AW & Lammertsma, K 2018, 'Chiral Control in Pentacoordinate Systems: The Case of Organosilicates' Inorganic Chemistry, vol. 57, no. 20, pp. 12697-12708. https://doi.org/10.1021/acs.inorgchem.8b01861

Chiral Control in Pentacoordinate Systems : The Case of Organosilicates. / Van Der Boon, Leon J.P.; Van Gelderen, Laurens; De Groot, Tim R.; Lutz, Martin; Slootweg, J. Chris; Ehlers, Andreas W.; Lammertsma, Koop.

In: Inorganic Chemistry, Vol. 57, No. 20, 15.10.2018, p. 12697-12708.

Research output: Contribution to JournalArticleAcademicpeer-review

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Van Der Boon LJP, Van Gelderen L, De Groot TR, Lutz M, Slootweg JC, Ehlers AW et al. Chiral Control in Pentacoordinate Systems: The Case of Organosilicates. Inorganic Chemistry. 2018 Oct 15;57(20):12697-12708. https://doi.org/10.1021/acs.inorgchem.8b01861