Mechanochemical synthesis of an organometallic compound: a high volume manufacturing method

Abstract

Chemical vapor deposition (CVD) precursor chemicals are held to some of the highest purity levels in industry. Many metal reagents form stable, unbreakable adducts with the coordinating solvents that are necessary for solvating highly polar reagents. These adducts are undesirable and must be removed prior to usage. Herein we describe a mechanochemical approach to the synthesis of bis(n-propyltetramethylcyclopentadienyl)strontium that eliminates the use of strongly coordinating solvents. This method overcomes the solubility problems of the two reagents without the formation of stable, unbreakable adducts. We utilize a unique reactor geometry that facilitates mechanochemical syntheses while simplifying handling and allowing for "one pot" production. The synthesis was scaled to five hundred gram lot sizes in a six liter reactor. This technique is applicable to many syntheses and is linearly scalable - limited only by reactor size.

Systematic studies on mechanochemical synthesis: Schiff bases from solid aromatic primary amines and aldehydes

“…In a recent Faraday discussion‐themed issue on “ Mechanochemistry: From Functional Solids to Single Molecules, ” the mechanochemistry of organic molecules, soft materials and pharmaceuticals, the mechanochemistry of inorganic compounds and coordination‐based materials, sonication and macromolecular mechanochemistry, current theoretical models for mechanochemical reactions, the mechanistic and kinetic understanding, catalysis, and scaling up of mechanochemistry were broadly discussed …”

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.…”

Main group mechanochemistry: from curiosity to established protocols

“…9). 22 In this way, the product was obtained in high yields within a few hours (88% isolated yield) and was readily scalable (up to 500 g); although the steel-on-glass reactor used showed signs of erosion upon prolonged milling.…”

“…Another example within the organometallic family is the synthesis of a strontium complex that can act as a chemical vapor deposition (CVD) precursor to strontium-based semiconductors. 22 In solution, Sr(Cp 0 ) 2 (Cp 0 = n-propyltetramethylcyclopentadiene) is typically synthesised via a salt metathesis reaction between alkali metal cyclopentadienides (i.e., KCp 0 ) and metal halides (e.g., SrI 2 ). However, this reaction is hindered by the low solubility of strontium iodide in solvents compatible with the air-and water-sensitive nature of reagents and products (i.e., Cp 0 salts).…”