A multi-step solvent-free mechanochemical route to indium(iii) complexes

Abstract

Mechanochemistry is well-established in the solid-phase synthesis of inorganic materials but has rarely been employed for molecular syntheses. In recent years, there has been nascent interest in 'greener' synthetic methods with less solvent, higher yields, and shorter reaction times being especially appealing to the fine chemicals and inorganic catalyst industries. Herein, we demonstrate that main-group indium(iii) complexes featuring bis(imino)acenaphthene (BIAN) ligands are readily accessible through a mechanochemical milling approach. The synthetic methodology reported herein not only bypasses the use of large solvent quantities and transition metal reagents for ligand synthesis, but also reduces reaction times dramatically. These new main-group complexes exhibit the potential to be reduced to indium(i) compounds, which may be employed as photosensitizers in organic catalyses and functional materials.

Mechanochemical Synthesis of Phosphazane‐Based Frameworks

“…[12,13] In its broadest terms, mechanochemistrydates back two millennia; [14] however,o nly in recent decadesh as it experienced ar enaissance. [18][19][20][21][22][23][24][25][26] Despite its long history and recents uccesses, these methodologies remain largely unexploredf or the synthesis of main-group compounds, with only works by Peters et al [27] andH anusa et al [22,28] on organometallic complexes.W er ecently reported af ast and high-yielding, multi-step, orthogonal mechanochemicals ynthesis of indium(III)c omplexes, [29] and demonstrated the value of this technique in enabling the isomerisation of as terically encumbered phosphazane. [18][19][20][21][22][23][24][25][26] Despite its long history and recents uccesses, these methodologies remain largely unexploredf or the synthesis of main-group compounds, with only works by Peters et al [27] andH anusa et al [22,28] on organometallic complexes.W er ecently reported af ast and high-yielding, multi-step, orthogonal mechanochemicals ynthesis of indium(III)c omplexes, [29] and demonstrated the value of this technique in enabling the isomerisation of as terically encumbered phosphazane.…”

Mechanosynthesis of a Copper complex for redox initiating systems with a unique near infrared light activation

“…One can question the problem caused by these drops of solvent: for a scale up, the presence of solvent will lead to significant emissions of VOCs. Also, the planetary milling is seen as a possible way to automate (and hence upscale) the grinding processes but the use of drops of solvent inside a closed jar can result in high risks of explosion. As a result, here, we propose to use a copper complex obtained by a full solvent‐free mechanosynthesis in redox and light activated redox polymerization.…”

Reaction of PdCl2 with Diphenylacetylene Revisited: Effect of Solvents and Ball Milling on Cyclization and Crystal Structures of Dimeric Cyclobutenylpalladium Chloride Complexes

“…The recent advancement in solvent free green chemical methods for the synthesis of inorganic complexes prompted us to explore these reactions under ball‐milling conditions using solvent free conditions ,,. Initial attempt to directly synthesize π ‐tetraphenylcyclobutadienepalladium(II) chloride, [{ π ‐Ph 4 C 4 }PdCl 2 ] 2 by reacting PdCl 2 and diphenylacetylene in 1:2 ratio under ball‐milling at 450 rpm for 4 hours yielded hexaphenylbenzene via 2+2+2 cyclic trimerization of diphenylacetylene and unreacted PdCl 2 was recovered.…”