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

doi:10.1002/ejic.201900641

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

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-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 language	English
Pages (from-to)	3318-3328
Number of pages	11
Journal	European Journal of Inorganic Chemistry
Volume	2019
Issue number	28
Early online date	7 Jul 2019
DOIs	https://doi.org/10.1002/ejic.201900641
Publication status	Published - 31 Jul 2019

Funding

This work was supported by The Netherlands Organisation for Scientific Research, Chemical Sciences (NWO-CW). We acknowledge SARA Computing and Networking Services for computer time.

Funders	Funder number
Chemical Sciences
NWO-CW
Commonwealth Scientific and Industrial Research Organisation
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

Keywords

Berry pseudorotation
Density functional calculations
Hypervalent compounds
Silicates
Silicon

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/ejic.201900641

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Cite this

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title = "Dynamic Conformational Behavior in Stable Pentaorganosilicates",

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.",

keywords = "Berry pseudorotation, Density functional calculations, Hypervalent compounds, Silicates, Silicon",

author = "{van der Boon}, {Leon J.P.} and Hendriks, {Jesper H.} and Danny Roolvink and O'Kennedy, {Sean J.} and Martin Lutz and Slootweg, {J. Chris} and Ehlers, {Andreas W.} and Koop Lammertsma",

year = "2019",

month = jul,

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doi = "10.1002/ejic.201900641",

language = "English",

volume = "2019",

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AU - van der Boon, Leon J.P.

AU - Hendriks, Jesper H.

AU - Roolvink, Danny

AU - O'Kennedy, Sean J.

AU - Lutz, Martin

AU - Slootweg, J. Chris

AU - Ehlers, Andreas W.

AU - Lammertsma, Koop

PY - 2019/7/31

Y1 - 2019/7/31

N2 - 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.

AB - 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.

KW - Berry pseudorotation

KW - Density functional calculations

KW - Hypervalent compounds

KW - Silicates

KW - Silicon

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Dynamic Conformational Behavior in Stable Pentaorganosilicates

Abstract

Funding

Keywords

UN SDGs

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CCDC 1901695: Experimental Crystal Structure Determination

CCDC 1901694: Experimental Crystal Structure Determination

CCDC 1901693: Experimental Crystal Structure Determination

Cite this

Dynamic Conformational Behavior in Stable Pentaorganosilicates

Abstract

Funding

Keywords

UN SDGs

Access to Document

Persistent URL (handle)

Other files and links

Fingerprint

Datasets

CCDC 1901695: Experimental Crystal Structure Determination

CCDC 1901694: Experimental Crystal Structure Determination

CCDC 1901693: Experimental Crystal Structure Determination

Cite this