Alkylzinc-Mediated Transmetallation of a Calcium Hydride

Kyle G. Pearce; Mary F. Mahon; Michael S. Hill

doi:10.1039/D5DT00958H

Alkylzinc-Mediated Transmetallation of a Calcium Hydride

Kyle G. Pearce, Mary F. Mahon, Michael S. Hill

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

2 Citations (SciVal)

Abstract

The dimeric β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CNDipp}2; Dipp = 2,6-i-Pr2C6H3), reacts with dialkylzinc reagents in a 1:2 ratio through sequential dialkyl(hydrido)zincate formation, calcium alkyl extrusion followed by further irreversible transmetallation of both the organyl and spectator BDI ligands, demonstrating the generality of this transmetallation strategy to access calcium alkyls or ligated zinc alkylated species. When the reaction is performed with dimethyl zinc and an organocalcium dimer with a pre-installed kinetically stabilising aryl substituent, [(BDI)Ca(μ-3,5-tBu2C6H3)(μ-H)Ca(BDI)], an organocalcium dimer comprised of differentiated alkyl and aryl functionalities can be accessed through hydride-for-methyl exchange, [(BDI)Ca(μ-3,5-tBu2C6H3)(μ-Me)Ca(BDI)].

Original language	English
Pages (from-to)	8903-8907
Number of pages	5
Journal	Dalton Transactions
Volume	54
Issue number	22
Early online date	6 May 2025
DOIs	https://doi.org/10.1039/D5DT00958H
Publication status	Published - 7 May 2025

Data Availability Statement

Experimental details, NMR spectra and details of the X-ray crystallographic analysis can be found in the ESI.† Crystallographic data for all compounds have been deposited with the Cambridge Crystallographic Data Centre as supplementary publications CCDC 2430071–2430073 for 6, 7 and 9, respectively.

Funding

The authors acknowledge EPSRC (EP/X01181X/1, \u2018Molecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements\u2019).

Funders	Funder number
Engineering and Physical Sciences Research Council	EP/X01181X/1

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10.1039/D5DT00958HLicence: CC BY

Cite this

@article{0c36c9b492b04591a33a1a92104ce8fe,

title = "Alkylzinc-Mediated Transmetallation of a Calcium Hydride",

abstract = "The dimeric β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC\{(Me)CNDipp\}2; Dipp = 2,6-i-Pr2C6H3), reacts with dialkylzinc reagents in a 1:2 ratio through sequential dialkyl(hydrido)zincate formation, calcium alkyl extrusion followed by further irreversible transmetallation of both the organyl and spectator BDI ligands, demonstrating the generality of this transmetallation strategy to access calcium alkyls or ligated zinc alkylated species. When the reaction is performed with dimethyl zinc and an organocalcium dimer with a pre-installed kinetically stabilising aryl substituent, [(BDI)Ca(μ-3,5-tBu2C6H3)(μ-H)Ca(BDI)], an organocalcium dimer comprised of differentiated alkyl and aryl functionalities can be accessed through hydride-for-methyl exchange, [(BDI)Ca(μ-3,5-tBu2C6H3)(μ-Me)Ca(BDI)].",

author = "Pearce, \{Kyle G.\} and Mahon, \{Mary F.\} and Hill, \{Michael S.\}",

year = "2025",

month = may,

day = "7",

doi = "10.1039/D5DT00958H",

language = "English",

volume = "54",

pages = "8903--8907",

journal = "Dalton Transactions ",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "22",

}

TY - JOUR

T1 - Alkylzinc-Mediated Transmetallation of a Calcium Hydride

AU - Pearce, Kyle G.

AU - Mahon, Mary F.

AU - Hill, Michael S.

PY - 2025/5/7

Y1 - 2025/5/7

N2 - The dimeric β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CNDipp}2; Dipp = 2,6-i-Pr2C6H3), reacts with dialkylzinc reagents in a 1:2 ratio through sequential dialkyl(hydrido)zincate formation, calcium alkyl extrusion followed by further irreversible transmetallation of both the organyl and spectator BDI ligands, demonstrating the generality of this transmetallation strategy to access calcium alkyls or ligated zinc alkylated species. When the reaction is performed with dimethyl zinc and an organocalcium dimer with a pre-installed kinetically stabilising aryl substituent, [(BDI)Ca(μ-3,5-tBu2C6H3)(μ-H)Ca(BDI)], an organocalcium dimer comprised of differentiated alkyl and aryl functionalities can be accessed through hydride-for-methyl exchange, [(BDI)Ca(μ-3,5-tBu2C6H3)(μ-Me)Ca(BDI)].

AB - The dimeric β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CNDipp}2; Dipp = 2,6-i-Pr2C6H3), reacts with dialkylzinc reagents in a 1:2 ratio through sequential dialkyl(hydrido)zincate formation, calcium alkyl extrusion followed by further irreversible transmetallation of both the organyl and spectator BDI ligands, demonstrating the generality of this transmetallation strategy to access calcium alkyls or ligated zinc alkylated species. When the reaction is performed with dimethyl zinc and an organocalcium dimer with a pre-installed kinetically stabilising aryl substituent, [(BDI)Ca(μ-3,5-tBu2C6H3)(μ-H)Ca(BDI)], an organocalcium dimer comprised of differentiated alkyl and aryl functionalities can be accessed through hydride-for-methyl exchange, [(BDI)Ca(μ-3,5-tBu2C6H3)(μ-Me)Ca(BDI)].

UR - https://www.scopus.com/pages/publications/105005292141

U2 - 10.1039/D5DT00958H

DO - 10.1039/D5DT00958H

M3 - Article

SN - 1477-9226

VL - 54

SP - 8903

EP - 8907

JO - Dalton Transactions

JF - Dalton Transactions

IS - 22

ER -

Alkylzinc-Mediated Transmetallation of a Calcium Hydride

Abstract

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

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Alkylzinc-Mediated Transmetallation of a Calcium Hydride

Abstract

Data Availability Statement

Funding

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

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