PRECISION SMOM · Precision Synthesis and Catalysis using Solid-State Molecular Organometallic Chemistry. Single-Crystal Reactivity in 3D and 2D

Fast and efficient solution-based homogeneous catalysis, or the synthesis of complexes with weakly bound ligands (e.g. methane), often requires the formation of a highly active, coordinatively unsaturated, metal centre. However, the vast excess of solvent can play a detrimental role by competitive coordination, or reaction itself, at the metal centre. Even if solvent does not impede the formation of reactive species, dimerisation can form inactive complexes. These factors quench reactivity and obstruct the formation of reactive complexes that are on the brink of stability, but at the cutting-edge of synthesis and catalysis.If the problem is the solution, then the solution is to remove the solution!PRECISION SMOM directly addresses this problem, redefining what is possible in the molecular synthesis of, and catalysis with, highly active organometallic complexes, by offering opportunities in chemical space that extend far beyond what is possible using solution-based methods. It does this by exploiting the Solid-state Molecular OrganoMetallic (SMOM) methods pioneered by Weller; where synthesis, reactivity and catalysis occur in crystallo using precisely-defined molecular single-crystals in solid/gas processes, as shown by the synthesis and reactivity of stable σ-alkane complexes, solving a 40-yr-old challenge in organometallic chemistry.PRECISION SMOM will use a suite of synergistic studies to understand, and control, the influence of metal site and microenvironment on in crystallo reactivity. Such holistic, fundamental, understanding will promote the translation of SMOM systems into precisely-defined heterogeneous molecular catalysis, focussing on selective and efficient processes for a range of challenging but widely applicable transformations. PRECISION SMOM will change the way we think about reactivity in molecular single-crystals: breaking new ground, embracing wider challenges, and exploiting new opportunities for in crystallo synthesis and catalysis.