Nucleophilic Triphenylgermanides of Magnesium and Calcium

Dominic B. Kennedy; Kyle G. Pearce; Louis J. Morris; Mary Mahon; Cameron Jones; Michael S. Hill

doi:10.1002/chem.202404160

Nucleophilic Triphenylgermanides of Magnesium and Calcium

Dominic B. Kennedy, Kyle G. Pearce, Louis J. Morris, Mary Mahon, Cameron Jones, Michael S. Hill

Monash University

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

Abstract

The dimeric calcium and magnesium hydrides, [(BDI)AeH]2 [BDI=HC{(Me)CNDipp}2, Dipp=2,6-i-Pr2C6H3; Ae=Mg or Ca] do not react with Ph3GeH in non-coordinating solvent. Addition of THF, however, induces deprotonation and access to monomeric Ae-germanide complexes, [(BDI)Ae{GePh3}(THF)], both of which have been structurally characterized. Although this process is facile when Ae=Ca, the analogous magnesium-based reaction requires heating to temperatures >100 °C, under which conditions germanide formation is complicated by THF ring opening and the generation of an alkaline earth germyl-C-terminated n-butoxide, [(BDI)Mg{μ2-O(CH2)4GePh3}]. Reactions of [(BDI)Ca{GePh3}(THF)] with N,N′-di-isopropylcarbodiimide and benzophenone provide the respective germylamidinate and germylalkoxide derivatives, [(BDI)Ca{(i-PrN)2CGePh3}(THF)] and [(BDI)Ca{OC(GePh3)Ph2}(THF)], demonstrating its potential as a well-defined and soluble source of the [Ph3Ge]− anion in nucleophilic addition reactions.

Original language	English
Article number	e202404160
Journal	Chemistry - A European Journal
Early online date	2 Dec 2024
DOIs	https://doi.org/10.1002/chem.202404160
Publication status	E-pub ahead of print - 2 Dec 2024

Data Availability Statement

The data that support the findings of this study are available in the supplementary material of this article.

Funding

The EPSRC is thanked for financial support (grant EP/X01181X/1) of this research. DBK thanks the Monash/Bath joint PhD program for funding. CJ is grateful to the Australian Research Council and the US Air Force Asian Office of Aerospace Research and Development (grant FA2386\u201021\u20101\u20104048) for funding aspects of this work.

Funders	Funder number
Australian Research Council
Engineering and Physical Sciences Research Council	EP/X01181X/1
Engineering and Physical Sciences Research Council
US Air Force Asian Office of Aerospace Research and Development	FA2386‐21‐1‐4048

Keywords

calclium
germanide
magnesium
nucleophile
triphenylgermane

ASJC Scopus subject areas

Catalysis
General Chemistry
Organic Chemistry

Access to Document

10.1002/chem.202404160Licence: CC BY

Cite this

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title = "Nucleophilic Triphenylgermanides of Magnesium and Calcium",

abstract = "The dimeric calcium and magnesium hydrides, [(BDI)AeH]2 [BDI=HC{(Me)CNDipp}2, Dipp=2,6-i-Pr2C6H3; Ae=Mg or Ca] do not react with Ph3GeH in non-coordinating solvent. Addition of THF, however, induces deprotonation and access to monomeric Ae-germanide complexes, [(BDI)Ae{GePh3}(THF)], both of which have been structurally characterized. Although this process is facile when Ae=Ca, the analogous magnesium-based reaction requires heating to temperatures >100 °C, under which conditions germanide formation is complicated by THF ring opening and the generation of an alkaline earth germyl-C-terminated n-butoxide, [(BDI)Mg{μ2-O(CH2)4GePh3}]. Reactions of [(BDI)Ca{GePh3}(THF)] with N,N′-di-isopropylcarbodiimide and benzophenone provide the respective germylamidinate and germylalkoxide derivatives, [(BDI)Ca{(i-PrN)2CGePh3}(THF)] and [(BDI)Ca{OC(GePh3)Ph2}(THF)], demonstrating its potential as a well-defined and soluble source of the [Ph3Ge]− anion in nucleophilic addition reactions.",

keywords = "calclium, germanide, magnesium, nucleophile, triphenylgermane",

author = "Kennedy, {Dominic B.} and Pearce, {Kyle G.} and Morris, {Louis J.} and Mary Mahon and Cameron Jones and Hill, {Michael S.}",

year = "2024",

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doi = "10.1002/chem.202404160",

language = "English",

journal = "Chemistry - A European Journal",

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AU - Kennedy, Dominic B.

AU - Pearce, Kyle G.

AU - Morris, Louis J.

AU - Mahon, Mary

AU - Jones, Cameron

AU - Hill, Michael S.

PY - 2024/12/2

Y1 - 2024/12/2

N2 - The dimeric calcium and magnesium hydrides, [(BDI)AeH]2 [BDI=HC{(Me)CNDipp}2, Dipp=2,6-i-Pr2C6H3; Ae=Mg or Ca] do not react with Ph3GeH in non-coordinating solvent. Addition of THF, however, induces deprotonation and access to monomeric Ae-germanide complexes, [(BDI)Ae{GePh3}(THF)], both of which have been structurally characterized. Although this process is facile when Ae=Ca, the analogous magnesium-based reaction requires heating to temperatures >100 °C, under which conditions germanide formation is complicated by THF ring opening and the generation of an alkaline earth germyl-C-terminated n-butoxide, [(BDI)Mg{μ2-O(CH2)4GePh3}]. Reactions of [(BDI)Ca{GePh3}(THF)] with N,N′-di-isopropylcarbodiimide and benzophenone provide the respective germylamidinate and germylalkoxide derivatives, [(BDI)Ca{(i-PrN)2CGePh3}(THF)] and [(BDI)Ca{OC(GePh3)Ph2}(THF)], demonstrating its potential as a well-defined and soluble source of the [Ph3Ge]− anion in nucleophilic addition reactions.

AB - The dimeric calcium and magnesium hydrides, [(BDI)AeH]2 [BDI=HC{(Me)CNDipp}2, Dipp=2,6-i-Pr2C6H3; Ae=Mg or Ca] do not react with Ph3GeH in non-coordinating solvent. Addition of THF, however, induces deprotonation and access to monomeric Ae-germanide complexes, [(BDI)Ae{GePh3}(THF)], both of which have been structurally characterized. Although this process is facile when Ae=Ca, the analogous magnesium-based reaction requires heating to temperatures >100 °C, under which conditions germanide formation is complicated by THF ring opening and the generation of an alkaline earth germyl-C-terminated n-butoxide, [(BDI)Mg{μ2-O(CH2)4GePh3}]. Reactions of [(BDI)Ca{GePh3}(THF)] with N,N′-di-isopropylcarbodiimide and benzophenone provide the respective germylamidinate and germylalkoxide derivatives, [(BDI)Ca{(i-PrN)2CGePh3}(THF)] and [(BDI)Ca{OC(GePh3)Ph2}(THF)], demonstrating its potential as a well-defined and soluble source of the [Ph3Ge]− anion in nucleophilic addition reactions.

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KW - germanide

KW - magnesium

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KW - triphenylgermane

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Nucleophilic Triphenylgermanides of Magnesium and Calcium

Abstract

Data Availability Statement

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Molecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements

Nucleophilic alkaline earth boryls: from conception and theory to application

Cite this

Nucleophilic Triphenylgermanides of Magnesium and Calcium

Abstract

Data Availability Statement

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

Molecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements

Nucleophilic alkaline earth boryls: from conception and theory to application

Cite this