Lanthanide organometallic chemistry has traditionally been defined by ligands that create near-saturated coordination spheres. In such cases, 2-3 open coordination sites allow for substrate coordination and transformation. We have been examining lanthanide complexes whose coordination spheres are influenced by non-covalent interactions such C-F-->M and hydrogen bonding. The C-F--> interactions serve as both precursors along the reaction coordinate for C-F activation and as structural elements for the synthesis of complexes with 'reserved' coordination sites. Hydrogen bonding between ligands has been discovered to lend air and moisture stability to asymmetric Lewis acid precatalysis. The air stable compounds are poised to increase the utility of lanthanides in diverse catalytic reaction classes.

New organo-f-element chemistry enabled by noncovalent interactions

248th National Meeting (2014)

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