Synthesis, Structure, and Reactivity of a Superbulky low-Valent β-diketiminate Ga(I) Complex

Richter T, Thum S, Townrow O, Wiesinger M, Langer J, Harder S (2024)

Publication Type: Journal article

Publication year: 2024

Journal

Zeitschrift für Anorganische und Allgemeine Chemie Wiley

DOI: 10.1002/zaac.202400044

Abstract

A low-valent GaI complex with the superbulky β-diketiminate ligand DIPePBDI (HC[C(Me)N−DIPeP]2, DIPeP=2,6-C(H)Et2-phenyl)) was obtained by reduction of (DIPePBDI)GaI2 (1) with KC8 in toluene. Considering that (BDI)GaI and analogue (BDI)AlI complexes are prone to decomposition and can generally only be obtained in low yields (20–40 %), the quantitative formation of (DIPePBDI)GaI (2) is remarkable and no doubt related to its excellent thermal stability even in refluxing toluene. Although the low-valent metal center in 2 is sterically protected by the superbulky DIPePBDI ligand, it is readily oxidized by N2O to give intermediate (DIPePBDI)Ga=O which readily decomposed by abstracting a proton from the backbone Me-substituent. Reaction with trimethylsilyl azide gave an intermediate imido complex (DIPePBDI)Ga=N(SiMe3)2 which reacted with a second equivalent of Me3SiN3 to a mixture of an azide/amido complex (DIPePBDI)GaN3[N(SiMe3)2] (4) and a tetrazagallole complex (DIPePBDI)Ga[N4(SiMe3)2] (5) in a 1 : 2 ratio. Whereas the azide/amido complex 4 could be structurally characterised, the tetraazagallole complex 5 was identified by NMR spectroscopy. DFT calculations on (DIPePBDI)GaI (2) and its reaction products complement this study.

Authors with CRIS profile

Tim Richter Lehrstuhl für Anorganische und Metallorganische Chemie Stefan Thum Lehrstuhl für Anorganische und Metallorganische Chemie Oliver Townrow Lehrstuhl für Anorganische und Metallorganische Chemie Michael Wiesinger Lehrstuhl für Anorganische und Metallorganische Chemie Jens Langer Lehrstuhl für Anorganische und Metallorganische Chemie Sjoerd Harder Lehrstuhl für Anorganische und Metallorganische Chemie

How to cite

APA:

Richter, T., Thum, S., Townrow, O., Wiesinger, M., Langer, J., & Harder, S. (2024). Synthesis, Structure, and Reactivity of a Superbulky low-Valent β-diketiminate Ga(I) Complex. Zeitschrift für Anorganische und Allgemeine Chemie. https://doi.org/10.1002/zaac.202400044

MLA:

Richter, Tim, et al. "Synthesis, Structure, and Reactivity of a Superbulky low-Valent β-diketiminate Ga(I) Complex." Zeitschrift für Anorganische und Allgemeine Chemie (2024).

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