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1H-NMR spectra is approximately 1:1 (see the Supporting Information, page-S15). Furthermore, it was interesting to find that the alkyl indium reagent 2 a could decompose when THF was completely removed under reduced pressure or when it was purified by silica-gel column chromatography. Therefore, the presence of THF might play an important role in the stabilization of the alkyl indium reagent 2 a by coordinating with the indium center. Thus, the following structure was proposed for the alkyl indium reagent 2 a. For related crystal structures of organoindium reagents with a halide bridge and five-coordinated indium center, see
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The following solvents were screened for the conversion of 1-(2-bromoethyl)benzene to the corresponding alkyl indium reagent: THF, 65 °C, 24-h, <5 % yield; 1,4-dioxane, 100 °C, 24-h, 38 % yield; DMA, 100 °C, 24-h, >90 % yield; DMF, 100 °C, 24-h, >90 % yield. Considering that the subsequent palladium-catalyzed coupling reaction should be carried out in DMA, this was chosen as reaction solvent for the formation of the alkyl indium reagent from alkyl bromide.
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