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A Hydride‐Substituted Homoleptic Silylborate: How Similar is it to its Diborane(6)‐Dianion Isostere?

Gilmer, Jannik, Bolte, Michael, Virovets, Alexander, Lerner, Hans‐Wolfram, Fantuzzi, Felipe, Wagner, Matthias (2022) A Hydride‐Substituted Homoleptic Silylborate: How Similar is it to its Diborane(6)‐Dianion Isostere? Chemistry – A European Journal, 29 (4). Article Number e202203119. ISSN 1521-3765. (doi:10.1002/chem.202203119) (KAR id:98477)

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The B‐nucleophilic 9H‐9‐borafluorene dianion reacts with 9‐chloro‐9‐silafluorene to afford air‐ and moisture‐stable silylborate salts M[Ar2(H)B−Si(H)Ar2] (M[HBSiH], M=Li, Na). Li[HBSiH] and Me3SiCl give the B−pyridine adduct Ar2(py)B−Si(H)Ar2 ((py)BSiH) or the chlorosilane Li[Ar2(H)B−Si(Cl)Ar2] (Li[HBSiCl]) in C6H6‐pyridine or THF. In both cases, the first step is H− abstraction at the B center. The resulting free borane subsequently binds a py or thf ligand. While the py adduct is stable at room temperature, the thf adduct undergoes a 1,2‐H shift via the cyclic B(μ‐H)Si intermediate BHSi, which is afterwards attacked at the Si atom by a Cl− ion to give Li[HBSiCl]. DFT calculations were employed to support the proposed reaction mechanism and to characterize the electronic structure of BHSi. Treatment of Li[HBSiCl] with the N‐heterocyclic carbene IMe introduces the neutral donor at the Si atom and leads to Ar2(H)B−Si(IMe)Ar2 (HBSi(IMe)), a donor‐acceptor‐stabilized silylene.

Item Type: Article
DOI/Identification number: 10.1002/chem.202203119
Uncontrolled keywords: Research Article, Research Articles, diagonal relationship, hydride abstraction, silylborane, subvalent compounds, umpolung
Subjects: Q Science > QD Chemistry
Divisions: Divisions > Division of Natural Sciences > Chemistry and Forensics
SWORD Depositor: JISC Publications Router
Depositing User: JISC Publications Router
Date Deposited: 30 Nov 2022 11:43 UTC
Last Modified: 01 Feb 2023 14:17 UTC
Resource URI: (The current URI for this page, for reference purposes)
Bolte, Michael:
Virovets, Alexander:
Lerner, Hans‐Wolfram:
Fantuzzi, Felipe:
Wagner, Matthias:
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