Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions

Matthew J. Evans; Finlay M. Burke; Peter M. Chapple; J. Robin Fulton

doi:10.1021/acs.inorgchem.1c00971

Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions

Matthew J. Evans, Finlay M. Burke, Peter M. Chapple, J. Robin Fulton

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

16 Citations (Scopus)

Abstract

We report the synthesis of aromatic germanimines [(HMDS)2Ge═NAr] (Ar = Ph, Mes, Dipp; Mes = 2,4,6-Me3C6H2, Dipp = 2,6-iPr2C6H3) and an investigation into their associated reactivity. [(HMDS)2Ge═NPh] decomposes above -30 °C, while [(HMDS)2Ge═NDipp] engages in an intramolecular reaction at 60 °C. [(HMDS)2Ge═NMes] was shown to rearrange via a 1,3-silyl migration to give [(HMDS){(SiMe3)(Mes)N}Ge(NSiMe3)] in a 1:7 equilibrium mixture at room temperature. These latter germanimines react with unsaturated polar substrates such as CO2, ketones, and arylisocyanate via a [2 + 2] cycloaddition pathway.

Original language	English
Pages (from-to)	8293-8303
Number of pages	11
Journal	Inorganic Chemistry
Volume	60
Issue number	11
DOIs	https://doi.org/10.1021/acs.inorgchem.1c00971
Publication status	Published - 7 Jun 2021
Externally published	Yes

Access to Document

10.1021/acs.inorgchem.1c00971

Cite this

@article{2118cf2e4c934543a9d8c758ecd894b8,

title = "Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions",

abstract = "We report the synthesis of aromatic germanimines [(HMDS)2Ge═NAr] (Ar = Ph, Mes, Dipp; Mes = 2,4,6-Me3C6H2, Dipp = 2,6-iPr2C6H3) and an investigation into their associated reactivity. [(HMDS)2Ge═NPh] decomposes above -30 °C, while [(HMDS)2Ge═NDipp] engages in an intramolecular reaction at 60 °C. [(HMDS)2Ge═NMes] was shown to rearrange via a 1,3-silyl migration to give [(HMDS){(SiMe3)(Mes)N}Ge(NSiMe3)] in a 1:7 equilibrium mixture at room temperature. These latter germanimines react with unsaturated polar substrates such as CO2, ketones, and arylisocyanate via a [2 + 2] cycloaddition pathway.",

author = "Evans, {Matthew J.} and Burke, {Finlay M.} and Chapple, {Peter M.} and Fulton, {J. Robin}",

note = "Publisher Copyright: {\textcopyright} ",

year = "2021",

month = jun,

day = "7",

doi = "10.1021/acs.inorgchem.1c00971",

language = "English",

volume = "60",

pages = "8293--8303",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "11",

}

TY - JOUR

T1 - Synthesis and Reactivity of Acyclic Germanimines

T2 - Silyl Rearrangement and Cycloadditions

AU - Evans, Matthew J.

AU - Burke, Finlay M.

AU - Chapple, Peter M.

AU - Fulton, J. Robin

N1 - Publisher Copyright: ©

PY - 2021/6/7

Y1 - 2021/6/7

N2 - We report the synthesis of aromatic germanimines [(HMDS)2Ge═NAr] (Ar = Ph, Mes, Dipp; Mes = 2,4,6-Me3C6H2, Dipp = 2,6-iPr2C6H3) and an investigation into their associated reactivity. [(HMDS)2Ge═NPh] decomposes above -30 °C, while [(HMDS)2Ge═NDipp] engages in an intramolecular reaction at 60 °C. [(HMDS)2Ge═NMes] was shown to rearrange via a 1,3-silyl migration to give [(HMDS){(SiMe3)(Mes)N}Ge(NSiMe3)] in a 1:7 equilibrium mixture at room temperature. These latter germanimines react with unsaturated polar substrates such as CO2, ketones, and arylisocyanate via a [2 + 2] cycloaddition pathway.

AB - We report the synthesis of aromatic germanimines [(HMDS)2Ge═NAr] (Ar = Ph, Mes, Dipp; Mes = 2,4,6-Me3C6H2, Dipp = 2,6-iPr2C6H3) and an investigation into their associated reactivity. [(HMDS)2Ge═NPh] decomposes above -30 °C, while [(HMDS)2Ge═NDipp] engages in an intramolecular reaction at 60 °C. [(HMDS)2Ge═NMes] was shown to rearrange via a 1,3-silyl migration to give [(HMDS){(SiMe3)(Mes)N}Ge(NSiMe3)] in a 1:7 equilibrium mixture at room temperature. These latter germanimines react with unsaturated polar substrates such as CO2, ketones, and arylisocyanate via a [2 + 2] cycloaddition pathway.

UR - http://www.scopus.com/inward/record.url?scp=85106365642&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.1c00971

DO - 10.1021/acs.inorgchem.1c00971

M3 - Article

C2 - 33988988

AN - SCOPUS:85106365642

SN - 0020-1669

VL - 60

SP - 8293

EP - 8303

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 11

ER -

Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions

Abstract

Access to Document

Other files and links

Cite this