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 language | English |
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Pages (from-to) | 12697-12708 |
Number of pages | 12 |
Journal | Inorganic Chemistry |
Volume | 57 |
Issue number | 20 |
Early online date | 2 Oct 2018 |
DOIs | |
Publication status | Published - 15 Oct 2018 |
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CCDC 1853539: Experimental Crystal Structure Determination
Van Der Boon, L. J. P. (Contributor), Van Gelderen, L. (Contributor), De Groot, T. R. (Contributor), Lutz, M. (Contributor), Slootweg, C. (Contributor), Ehlers, A. W. (Contributor) & Lammertsma, K. (Contributor), Unknown Publisher, 15 Oct 2018
DOI: 10.5517/ccdc.csd.cc206rll, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc206rll&sid=DataCite
Dataset
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CCDC 1853538: Experimental Crystal Structure Determination
Van Der Boon, L. J. P. (Contributor), Van Gelderen, L. (Contributor), De Groot, T. R. (Contributor), Lutz, M. (Contributor), Slootweg, C. (Contributor), Ehlers, A. W. (Contributor) & Lammertsma, K. (Contributor), Unknown Publisher, 15 Oct 2018
DOI: 10.5517/ccdc.csd.cc206rkk, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc206rkk&sid=DataCite
Dataset
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CCDC 1853537: Experimental Crystal Structure Determination
Van Der Boon, L. J. P. (Contributor), Van Gelderen, L. (Contributor), De Groot, T. R. (Contributor), Lutz, M. (Contributor), Slootweg, C. (Contributor), Ehlers, A. W. (Contributor) & Lammertsma, K. (Contributor), Unknown Publisher, 15 Oct 2018
DOI: 10.5517/ccdc.csd.cc206rjj, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc206rjj&sid=DataCite
Dataset