The gas-phase structure and some reactions of the bulky primary silane (Me3Si)3CSiH3 and the solid-state structure of the bulky dialkyl disilane [(Me3Si)3CSiH2]2

Masters, Sarah L.; Rankin, David W. H.; Cordes, David B.; Bätz, Karin; Lickiss, Paul D.; Boag, Neil M.; Redhouse, A. D.; Whittaker, Stephen M.

doi:10.1039/c0dt00100g

“…(Me 3 Si) 3 CSiH 3 was studied using both NMR spectroscopy and GED [33], while GED studies have also been carried out for (Me 3 Si) 3 CSiCl 3 [34], and for (HMe 2 Si) 3 CSiH 3 [35], which showed the presence of eleven distinct conformers.…”

Section: Introductionmentioning

confidence: 99%

Structures of Tetrasilylmethane Derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

Wann

¹

,

Robinson

²

,

Bätz

³

et al. 2015

J. Phys. Chem. A

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Article:Wann, Derek A. orcid.org/0000-0002-5495-274X, Robinson, Matthew S., Bätz, Karin et al. eprints@whiterose.ac.uk https://eprints.whiterose.ac.uk/ Reuse Unless indicated otherwise, fulltext items are protected by copyright with all rights reserved. The copyright exception in section 29 of the Copyright, Designs and Patents Act 1988 allows the making of a single copy solely for the purpose of non-commercial research or private study within the limits of fair dealing. The publisher or other rights-holder may allow further reproduction and re-use of this version -refer to the White Rose Research Online record for this item. Where records identify the publisher as the copyright holder, users can verify any specific terms of use on the publisher's website. TakedownIf you consider content in White Rose Research Online to be in breach of UK law, please notify us by emailing eprints@whiterose.ac.uk including the URL of the record and the reason for the withdrawal request. The structures of the molecules C(SiXMe 2 ) 4 (X = H, F, Cl, Br) have been determined by gas electron diffraction (GED). Ab initio calculations revealed nine potential minima for each species, with significant ranges of energies. For the H, F, Cl, and Br derivatives nine, seven, two, and two conformers were modelled, respectively, as they were quantum-chemically predicted to be present in measurable quantities. Variable-temperature 1 H and 29 Si solutionphase NMR studies and, where applicable, 13 C NMR, 1 H/ 29 Si NMR shift-correlation, and 1 H NMR saturation-transfer experiments are reported for C(SiXMe 2 ) 4 (X = H, Cl, Br, and also I).At low temperature in solution two conformers (one C 1 -symmetric and one C 2 -symmetric) are observed for each of C(SiXMe 2 ) 4 (X = Cl, Br, I), in agreement with the isolated molecule ab initio calculations carried out as part of this work for X = Cl, Br. C(SiHMe 2 ) 4 is present as a single C 1 -symmetric conformer in solution at the temperatures at which the NMR experiments were performed.

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Geometrically Compelled Silicon(II)/Silicon(IV) Donor–Acceptor Interaction Enables the Enamination of Nitriles

Kong,

Li,

Dai

et al. 2023

Angewandte Chemie

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Discovering new bonding scenarios and subsequently exploring the reactivity contribute substantially to advance the main group element chemistry. Herein, we report on the isolation and characterization of an intriguing class of the hydrido‐benzosiloles 2–4. These compounds exhibit a side arm of the amidinatosilylenyl group, featuring unidirectional silicon(II)/silicon(IV) donor‐acceptor interaction on account of the geometric constraint. Furthermore, the reactions involving 2–4 with nitriles yield the tricyclic compounds that edge‐fused of the Si‐heteroimidazolidine‐CN2Si2, silole‐C4Si, and phenyl‐C6‐rings (5–13). These compounds are manifesting a unique reaction that the silicon(II)/silicon(IV) interaction enables the enamination of the α‐H‐bearing nitriles. The reaction mechanism involved in H‐shift under oxidative addition at silylene followed by hydrosilylation of a ketenimine intermediate was revealed by density function theory (DFT) calculations.

show abstract

Geometrically Compelled Silicon(II)/Silicon(IV) Donor–Acceptor Interaction Enables the Enamination of Nitriles

Kong,

Li,

Dai

et al. 2023

Angew Chem Int Ed

0

View full text Add to dashboard Cite

Discovering new bonding scenarios and subsequently exploring the reactivity contribute substantially to advance the main group element chemistry. Herein, we report on the isolation and characterization of an intriguing class of the hydrido‐benzosiloles 2–4. These compounds exhibit a side arm of the amidinatosilylenyl group, featuring unidirectional silicon(II)/silicon(IV) donor‐acceptor interaction on account of the geometric constraint. Furthermore, the reactions involving 2–4 with nitriles yield the tricyclic compounds that edge‐fused of the Si‐heteroimidazolidine‐CN2Si2, silole‐C4Si, and phenyl‐C6‐rings (5–13). These compounds are manifesting a unique reaction that the silicon(II)/silicon(IV) interaction enables the enamination of the α‐H‐bearing nitriles. The reaction mechanism involved in H‐shift under oxidative addition at silylene followed by hydrosilylation of a ketenimine intermediate was revealed by density function theory (DFT) calculations.

show abstract

The gas-phase structure and some reactions of the bulky primary silane (Me3Si)3CSiH3 and the solid-state structure of the bulky dialkyl disilane [(Me3Si)3CSiH2]2

Cited by 5 publications

References 74 publications

Structures of Tetrasilylmethane Derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

Structures of Tetrasilylmethane Derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

Geometrically Compelled Silicon(II)/Silicon(IV) Donor–Acceptor Interaction Enables the Enamination of Nitriles

Geometrically Compelled Silicon(II)/Silicon(IV) Donor–Acceptor Interaction Enables the Enamination of Nitriles

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The gas-phase structure and some reactions of the bulky primary silane (Me3Si)3CSiH3 and the solid-state structure of the bulky dialkyl disilane [(Me3Si)3CSiH2]2

Cited by 5 publications

References 74 publications

Structures of Tetrasilylmethane Derivatives (XMe2Si)2C(SiMe3)2 (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

Structures of Tetrasilylmethane Derivatives (XMe2Si)2C(SiMe3)2 (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

Geometrically Compelled Silicon(II)/Silicon(IV) Donor–Acceptor Interaction Enables the Enamination of Nitriles

Geometrically Compelled Silicon(II)/Silicon(IV) Donor–Acceptor Interaction Enables the Enamination of Nitriles

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Product

Resources

About

Structures of Tetrasilylmethane Derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

Structures of Tetrasilylmethane Derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution