Solvent‐Dependent Oxidative Addition and Reductive Elimination of H2 Across a Gallium‐Zinc Bond

H2 adds reversibly across the metal‐metal bond of [(BDI)Ga(H)−Zn(tmeda)(thf)][BAr4F] (BDI=[HC{C(CH3)N(2,6‐iPr2‐C6H3)}2]−, TMEDA=N,N,N′,N′‐tetramethylethylenediamine, BAr4F−=[B(C6H3‐3,5‐(CF3)2)4]−). Due to the stabilising effect of solvent coordination, hydrogenation products [(BDI)GaH2] and [(tmeda)...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-09, Vol.61 (36), p.e202208855-n/a
Main Authors: Morris, Louis J., Rajeshkumar, Thayalan, Okumura, Akira, Maron, Laurent, Okuda, Jun
Format: Article
Language:English
Subjects:
Dehydrogenation
Gallium
Heterometallic Complexes
Hydrogenation
Main Group Compounds
Solvent Effects
Solvents
Zinc
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Summary:H2 adds reversibly across the metal‐metal bond of [(BDI)Ga(H)−Zn(tmeda)(thf)][BAr4F] (BDI=[HC{C(CH3)N(2,6‐iPr2‐C6H3)}2]−, TMEDA=N,N,N′,N′‐tetramethylethylenediamine, BAr4F−=[B(C6H3‐3,5‐(CF3)2)4]−). Due to the stabilising effect of solvent coordination, hydrogenation products [(BDI)GaH2] and [(tmeda)ZnH(thf)][BAr4F] are favoured in THF solution, but THF‐free mixtures of [(BDI)GaH2] and [(tmeda)ZnH(OEt2)][BAr4F] are predisposed towards entropically driven dehydrogenation to [(BDI)Ga(H)−Zn(tmeda)][BAr4F] in fluorobenzene solution. Dihydrogen reversibly adds across the Ga−Zn bond of a heterobimetallic cation. Oxidative addition is favoured in THF solution where the hydrogenation products are stabilized, but in fluorobenzene, reductive elimination of H2 is promoted by the Lewis‐acidic zinc hydride cation.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202208855