Activation of the Ga(I) cation for bond activation: from oxidative additions into C−Cl and H−P bonds to reversible insertion into P4
Abstract: Although the discovery of the GaI complex salt [Ga(PhF)2-3][Al(ORF)4] (RF=C(CF3)3, PhF=C6H5F) invoked the preparation of a diverse library of cationic Ga(I) coordination complexes and clusters, studies on small molecule activation with low-valent GaI cations are scarce. Herein, a first experimental study on the reactivity of a monomeric Ga(I) cation activated with a pyridine–diimine pincer ligand (in [Ga(PDIdipp)][Al(ORF)4]) towards small-molecules is reported. First controlled oxidative additions of the GaI cation into C−Cl, H−P and P−P bonds are presented. Moreover, the [4+1]cycloaddition to butadienes was achieved. Intriguingly, the isolated, blue insertion product into the P−P bond of P4 allows for the quantitative release of the P4 molecule upon reaction with AlEt3 and butadienes. Reversible P4 insertion of main-group metals has previously been reported for Ge and Sn, respectively. The experimental study is supported by high-level computational analysis of the in-part reversible oxidative additions at the DLPNO-CCSD(T)/def2-TZVPP//PBEh-3c/def2-mSVP level of theory with COSMO-RS solvation in 1,2-difluorobenzene
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Notes
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Chemistry – a European journal. - 29, 58 (2023) , e202302212, ISSN: 1521-3765
- Event
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Veröffentlichung
- (where)
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Freiburg
- (who)
-
Universität
- (when)
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2023
- Creator
- DOI
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10.1002/chem.202302212
- URN
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urn:nbn:de:bsz:25-freidok-2386957
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
-
25.03.2025, 1:55 PM CET
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Dabringhaus, Philipp
- Heizmann, Tim
- Krossing, Ingo
- Universität
Time of origin
- 2023
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