Dipyrromethene as a Ligand for the Stabilization of Low-Valent Gallium Complexes

Richter T, Thum S, Vilpas T, Townrow O, Klerner L, Langer J, Harder S (2024)

Publication Type: Journal article

Publication year: 2024

Journal

DOI: 10.1021/acs.organomet.4c00164

Abstract

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)Al^I by reduction of (^tBuDPM)AlI2 with KC8 failed. However, reduction of (^tBuDPM)GaI2 (1) with K/KI led to successful isolation of (^tBuDPM)Ga^I (3). The Ga^II 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)Ga^I 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.

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How to cite

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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