Synthesis and Reactivity of Bidentate N-Heterocyclic Carbene-Phosphinidene Supported Si(IV) Dicationic Complexes

Ramona Baierl; Arseni Kostenko; Franziska Hanusch; Alexander D. Beck; Shigeyoshi Inoue

doi:10.1002/ejoc.202201072

Synthesis and Reactivity of Bidentate N-Heterocyclic Carbene-Phosphinidene Supported Si(IV) Dicationic Complexes

Ramona Baierl, Arseni Kostenko, Franziska Hanusch, Alexander D. Beck, Shigeyoshi Inoue

Chair of Silicon Chemistry

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Herein, we report the synthesis and isolation of Si(IV) dications stabilized by a bidentate N-heterocyclic carbene-phosphinidene (NHCP). Treatment of the bis(NHCP) with Si(IV) bis(triflate) R₂Si(OTf)₂ (with R=H, Ph) resulted in the instant formation of Si(IV) dicationic complexes [2 a] and [2 b] featuring a tetracoordinated silicon centre. The dications show expected high Lewis acidity. The bis(NHCP)-stabilized parent silyl dication 2a (SiH₂²⁺) presents the first isolable example of a parent SiH₂ dication. In addition, dication [2 a] is able to react with diphenylketene by insertion into the Si−P bond.

Original language	English
Article number	e202201072
Journal	European Journal of Organic Chemistry
Volume	2022
Issue number	45
DOIs	https://doi.org/10.1002/ejoc.202201072
State	Published - 6 Dec 2022

Keywords

Coordination chemistry
Main group elements
N-Heterocyclic carbene-phosphinidene
Si(IV) Dications
Silanes

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10.1002/ejoc.202201072

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title = "Synthesis and Reactivity of Bidentate N-Heterocyclic Carbene-Phosphinidene Supported Si(IV) Dicationic Complexes",

abstract = "Herein, we report the synthesis and isolation of Si(IV) dications stabilized by a bidentate N-heterocyclic carbene-phosphinidene (NHCP). Treatment of the bis(NHCP) with Si(IV) bis(triflate) R2Si(OTf)2 (with R=H, Ph) resulted in the instant formation of Si(IV) dicationic complexes [2 a] and [2 b] featuring a tetracoordinated silicon centre. The dications show expected high Lewis acidity. The bis(NHCP)-stabilized parent silyl dication 2a (SiH22+) presents the first isolable example of a parent SiH2 dication. In addition, dication [2 a] is able to react with diphenylketene by insertion into the Si−P bond.",

keywords = "Coordination chemistry, Main group elements, N-Heterocyclic carbene-phosphinidene, Si(IV) Dications, Silanes",

author = "Ramona Baierl and Arseni Kostenko and Franziska Hanusch and Beck, {Alexander D.} and Shigeyoshi Inoue",

note = "Publisher Copyright: {\textcopyright} 2022 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH.",

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T1 - Synthesis and Reactivity of Bidentate N-Heterocyclic Carbene-Phosphinidene Supported Si(IV) Dicationic Complexes

AU - Baierl, Ramona

AU - Kostenko, Arseni

AU - Hanusch, Franziska

AU - Beck, Alexander D.

AU - Inoue, Shigeyoshi

PY - 2022/12/6

Y1 - 2022/12/6

N2 - Herein, we report the synthesis and isolation of Si(IV) dications stabilized by a bidentate N-heterocyclic carbene-phosphinidene (NHCP). Treatment of the bis(NHCP) with Si(IV) bis(triflate) R2Si(OTf)2 (with R=H, Ph) resulted in the instant formation of Si(IV) dicationic complexes [2 a] and [2 b] featuring a tetracoordinated silicon centre. The dications show expected high Lewis acidity. The bis(NHCP)-stabilized parent silyl dication 2a (SiH22+) presents the first isolable example of a parent SiH2 dication. In addition, dication [2 a] is able to react with diphenylketene by insertion into the Si−P bond.

AB - Herein, we report the synthesis and isolation of Si(IV) dications stabilized by a bidentate N-heterocyclic carbene-phosphinidene (NHCP). Treatment of the bis(NHCP) with Si(IV) bis(triflate) R2Si(OTf)2 (with R=H, Ph) resulted in the instant formation of Si(IV) dicationic complexes [2 a] and [2 b] featuring a tetracoordinated silicon centre. The dications show expected high Lewis acidity. The bis(NHCP)-stabilized parent silyl dication 2a (SiH22+) presents the first isolable example of a parent SiH2 dication. In addition, dication [2 a] is able to react with diphenylketene by insertion into the Si−P bond.

KW - Coordination chemistry

KW - Main group elements

KW - N-Heterocyclic carbene-phosphinidene

KW - Si(IV) Dications

KW - Silanes

UR - http://www.scopus.com/inward/record.url?scp=85143427832&partnerID=8YFLogxK

U2 - 10.1002/ejoc.202201072

DO - 10.1002/ejoc.202201072

M3 - Article

AN - SCOPUS:85143427832

SN - 1434-193X

VL - 2022

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 45

M1 - e202201072

ER -

Synthesis and Reactivity of Bidentate N-Heterocyclic Carbene-Phosphinidene Supported Si(IV) Dicationic Complexes

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Keywords

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