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

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2024-06-13 DOI:10.1021/acs.organomet.4c00164

Tim Richter, Stefan Thum, Timothy Vilpas, Oliver P. E. Townrow, Lukas Klerner, Jens Langer and Sjoerd Harder*,

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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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作为配体稳定低价镓络合物的二吡咯并乙烯

我们研究了铝和镓与配体 tBuDPM 的低价化学反应。tBuDPM 是一种二吡咯烷配体支架，在侧翼 1 位和 9 位有两个大的 tBu 基团，在骨架 5 位有一个间苯二酚基团。用 KC8 还原 (tBuDPM)AlI2 合成 (tBuDPM)AlI 的尝试失败了。然而，用 K/KI 还原 (tBuDPM)GaI2 (1) 却成功地分离出了 (tBuDPM)GaI (3)。还原过程中的 GaII 中间体结晶为二镓烷：(tBuDPM)GaI]2 (2)。此外，3 结晶为具有 Ga-Ga 键的双核复合物。然而，在苯溶液中，3 会解离成两个单核络合物。(tBuDPM)GaI 的苯溶液与过量的 Me3SiN3 反应生成了四氮唑产物 (tBuDPM)Ga[N4(SiMe3)2] (4)，而不是另一种叠氮酰胺产物 (tBuDPM)Ga(N3)[N(SiMe3)2] ，根据计算，后者在热力学上要稳定得多。此外，还对 2 和 3 中 Ga-Ga 键的性质以及 4 的选择性形成机制进行了理论研究。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.