NHC-Induced Dismutation of Gallium–Zinc bonds

Louis J. Morris; Clement G. Collins Rice; Dermot O’Hare

doi:10.1021/acs.organomet.6c00068

NHC-Induced Dismutation of Gallium–Zinc bonds

Louis J. Morris
, Clement G. Collins Rice
, Dermot O’Hare

Department of Chemistry

Chemistry Research Laboratory
University of Oxford

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

Abstract

The insertion of gallium(I) reagent [(BDI)Ga^I] (I, BDI = HC{C(CH₃)Ndipp}₂; dipp = 2,6-di-isopropyl-phenyl) into Zn^II–X bonds (X = OTf, Cl) to provide gallyl zinc complexes [(BDI)Ga(X)Zn(X)L₂] (1 – 3; L₂ = thf₂, tmeda; tmeda = N,N,N′,N′-tetramethylethylenediamine) is readily reversed by ligand substitution with an N-heterocyclic carbene (NHC), regenerating I and eliminating (NHC)_nZnX₂ via ‘dismutation’ of the Ga–Zn bond. The dative Ga→Zn interaction present in [(BDI)Ga·Zn(Cl)(tmeda)][BAr^F₄] (4; Ar^F = C₆H₃-3,5-(CF₃)₂) is similarly disrupted by the addition of NHC. [(BDI)Ga(X)Zn(X)L₂] complexes also react as a ‘masked’ source of I, as demonstrated by reactions with Et₃NHCl and B(C₆F₅)₃, which yield the respective literature compounds [(BDI)Ga(H)Cl] and [(BDI)Ga·B(C₆F₅)₃].

Original language	English
Pages (from-to)	1122-1127
Number of pages	6
Journal	Organometallics
Volume	45
Issue number	10
Early online date	13 May 2026
DOIs	https://doi.org/10.1021/acs.organomet.6c00068
Publication status	Published - 25 May 2026

Acknowledgements

The authors thank Chemical Crystallography (University of Oxford) for use of their diffractometers.

Funding

L.J.M. and C.G.C.R. thank SCG Chemicals Public Co. Limited for funding. L.J.M. also thanks the Leverhulme Trust (RPG2023−104, “Alkaline Element Z-type Ligands for Tunable Base Metal Catalysis”) and Prof. M. S. Hill for his generous support.

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{7968e0189091483fb5c9aa58b5cf7fa4,

title = "NHC-Induced Dismutation of Gallium{\textendash}Zinc bonds",

abstract = "The insertion of gallium(I) reagent [(BDI)GaI] (I, BDI = HC\{C(CH3)Ndipp\}2; dipp = 2,6-di-isopropyl-phenyl) into ZnII{\textendash}X bonds (X = OTf, Cl) to provide gallyl zinc complexes [(BDI)Ga(X)Zn(X)L2] (1 {\textendash} 3; L2 = thf2, tmeda; tmeda = N,N,N′,N′-tetramethylethylenediamine) is readily reversed by ligand substitution with an N-heterocyclic carbene (NHC), regenerating I and eliminating (NHC)nZnX2 via {\textquoteleft}dismutation{\textquoteright} of the Ga{\textendash}Zn bond. The dative Ga→Zn interaction present in [(BDI)Ga·Zn(Cl)(tmeda)][BArF4] (4; ArF = C6H3-3,5-(CF3)2) is similarly disrupted by the addition of NHC. [(BDI)Ga(X)Zn(X)L2] complexes also react as a {\textquoteleft}masked{\textquoteright} source of I, as demonstrated by reactions with Et3NHCl and B(C6F5)3, which yield the respective literature compounds [(BDI)Ga(H)Cl] and [(BDI)Ga·B(C6F5)3].",

author = "Morris, \{Louis J.\} and \{Collins Rice\}, \{Clement G.\} and Dermot O{\textquoteright}Hare",

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T1 - NHC-Induced Dismutation of Gallium–Zinc bonds

AU - Morris, Louis J.

AU - Collins Rice, Clement G.

AU - O’Hare, Dermot

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Y1 - 2026/5/25

N2 - The insertion of gallium(I) reagent [(BDI)GaI] (I, BDI = HC{C(CH3)Ndipp}2; dipp = 2,6-di-isopropyl-phenyl) into ZnII–X bonds (X = OTf, Cl) to provide gallyl zinc complexes [(BDI)Ga(X)Zn(X)L2] (1 – 3; L2 = thf2, tmeda; tmeda = N,N,N′,N′-tetramethylethylenediamine) is readily reversed by ligand substitution with an N-heterocyclic carbene (NHC), regenerating I and eliminating (NHC)nZnX2 via ‘dismutation’ of the Ga–Zn bond. The dative Ga→Zn interaction present in [(BDI)Ga·Zn(Cl)(tmeda)][BArF4] (4; ArF = C6H3-3,5-(CF3)2) is similarly disrupted by the addition of NHC. [(BDI)Ga(X)Zn(X)L2] complexes also react as a ‘masked’ source of I, as demonstrated by reactions with Et3NHCl and B(C6F5)3, which yield the respective literature compounds [(BDI)Ga(H)Cl] and [(BDI)Ga·B(C6F5)3].

AB - The insertion of gallium(I) reagent [(BDI)GaI] (I, BDI = HC{C(CH3)Ndipp}2; dipp = 2,6-di-isopropyl-phenyl) into ZnII–X bonds (X = OTf, Cl) to provide gallyl zinc complexes [(BDI)Ga(X)Zn(X)L2] (1 – 3; L2 = thf2, tmeda; tmeda = N,N,N′,N′-tetramethylethylenediamine) is readily reversed by ligand substitution with an N-heterocyclic carbene (NHC), regenerating I and eliminating (NHC)nZnX2 via ‘dismutation’ of the Ga–Zn bond. The dative Ga→Zn interaction present in [(BDI)Ga·Zn(Cl)(tmeda)][BArF4] (4; ArF = C6H3-3,5-(CF3)2) is similarly disrupted by the addition of NHC. [(BDI)Ga(X)Zn(X)L2] complexes also react as a ‘masked’ source of I, as demonstrated by reactions with Et3NHCl and B(C6F5)3, which yield the respective literature compounds [(BDI)Ga(H)Cl] and [(BDI)Ga·B(C6F5)3].

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AN - SCOPUS:105040010992

SN - 0276-7333

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JO - Organometallics

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ER -

NHC-Induced Dismutation of Gallium–Zinc bonds

Abstract

Acknowledgements

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