화학공학소재연구정보센터
Inorganic Chemistry, Vol.57, No.20, 12697-12708, 2018
Chiral Control in Pentacoordinate Systems: The Case of Organosilicates
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.