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

doi:10.1021/acs.inorgchem.8b01861

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

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-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 language	English
Pages (from-to)	12697-12708
Number of pages	12
Journal	Inorganic Chemistry
Volume	57
Issue number	20
Early online date	2 Oct 2018
DOIs	https://doi.org/10.1021/acs.inorgchem.8b01861
Publication status	Published - 15 Oct 2018

Access to Document

10.1021/acs.inorgchem.8b01861

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
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
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

Cite this

@article{d3bde243ee584c188c714c34604eda2d,

title = "Chiral Control in Pentacoordinate Systems: The Case of Organosilicates",

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.",

author = "{Van Der Boon}, {Leon J.P.} and {Van Gelderen}, Laurens and {De Groot}, {Tim R.} and Martin Lutz and Slootweg, {J. Chris} and Ehlers, {Andreas W.} and Koop Lammertsma",

year = "2018",

month = oct,

day = "15",

doi = "10.1021/acs.inorgchem.8b01861",

language = "English",

volume = "57",

pages = "12697--12708",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "20",

}

TY - JOUR

T1 - Chiral Control in Pentacoordinate Systems

T2 - The Case of Organosilicates

AU - Van Der Boon, Leon J.P.

AU - Van Gelderen, Laurens

AU - De Groot, Tim R.

AU - Lutz, Martin

AU - Slootweg, J. Chris

AU - Ehlers, Andreas W.

AU - Lammertsma, Koop

PY - 2018/10/15

Y1 - 2018/10/15

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85054378883&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85054378883&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.8b01861

DO - 10.1021/acs.inorgchem.8b01861

M3 - Article

C2 - 30277076

AN - SCOPUS:85054378883

VL - 57

SP - 12697

EP - 12708

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 20

ER -

Chiral Control in Pentacoordinate Systems: The Case of Organosilicates

Abstract

Access to Document

Fingerprint

Datasets

CCDC 1853537: Experimental Crystal Structure Determination

CCDC 1853538: Experimental Crystal Structure Determination

CCDC 1853539: Experimental Crystal Structure Determination

Cite this