A prerequisite for any inorganic/organometallic synthetic procedure is access to a suitable starting material. While low-valent, and high-valent species are typically either commercially available, or easy to access by established protocols, mid-valent synthons can be more challenging to prepare. Traditionally, high valent early transition metal halides are reduced in situ to form solvated complexes at the desired oxidation state or reacted with lower valent metal complexes to form the desired starting material via comproportionation. These routes can be challenging due to formation of unwanted byproducts, prolonged reaction times, and use of inorganic reducing agents that are difficult to prepare/handle (e.g. KC<sub>8</sub>, boron, aluminum or tin hydrides, Na/K, Na/Hg, etc.). Alternatively, utilizing the desired oxidation state metal halide presents its own challenges. Namely, such materials are accessed via high temperature routes, yielding crystalline solids which often display lower reactivity. We report here a facile solution-based route to uncoordinated early transition metal halides in high yield and purity. Utilizing relatively benign, commercially available hydridosilanes, we developed a simple reduction protocol to a broad library of inorganic synthons.

Facile synthesis of mid-valent early transition metal chlorides

ACS Spring 2022

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