Richter T, Thum S, Vilpas T, Townrow O, Klerner L, Langer J, Harder S (2024)
Publication Type: Journal article
Publication year: 2024
DOI: 10.1021/acs.organomet.4c00164
We investigated the low-valent chemistry of Al and Ga with the ligand tBuDPM, a dipyrromethene ligand scaffold with two large tBu groups in the flanking 1- and 9-positions and a mesityl group in the backbone 5-position. Attempted synthesis of (tBuDPM)AlI by reduction of (tBuDPM)AlI2 with KC8 failed. However, reduction of (tBuDPM)GaI2 (1) with K/KI led to successful isolation of (tBuDPM)GaI (3). The GaII intermediate in the reduction process crystallized as a digallane: [(tBuDPM)GaI]2 (2). Also, 3 crystallized as a dinuclear complex with a Ga-Ga bond. However, in a benzene solution, the 3 dissociates into two mononuclear complexes. Reaction of a benzene solution of (tBuDPM)GaI with excess Me3SiN3 gave the tetrazagallole product (tBuDPM)Ga[N4(SiMe3)2] (4) and not the alternative azide-amide product (tBuDPM)Ga(N3)[N(SiMe3)2], which according to calculations is thermodynamically considerably more stable. Theoretical investigations on the nature of the Ga-Ga bonds in 2 and 3 and the mechanism for selective formation of 4 have been included.
APA:
Richter, T., Thum, S., Vilpas, T., Townrow, O., Klerner, L., Langer, J., & Harder, S. (2024). Dipyrromethene as a Ligand for the Stabilization of Low-Valent Gallium Complexes. Organometallics. https://doi.org/10.1021/acs.organomet.4c00164
MLA:
Richter, Tim, et al. "Dipyrromethene as a Ligand for the Stabilization of Low-Valent Gallium Complexes." Organometallics (2024).
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