Rare earth organometallic chemistry has traditionally been dominated by simple carbocyclic frameworks; however, significant effort has recently been devoted to developing new scaffolds with different steric and electronic properties. Accordingly, we have designed a series of carbazole- and pyrrole-based pincer ligands that have proven effective in supporting metals spanning the periodic table. Although many of these species are thermally robust, others are prone to a variety of cyclometalation processes, especially those featuring larger metals, such as samarium. The synthesis and reaction chemistry of these organolanthanide complexes will be discussed in detail, with special attention dedicated to the unusual bonding modes and structures of the cyclometalated products. A family of new �cyclometalation-resistant� ligands will also be presented.

Intramolecular C�H activation in organometallic rare earth complexes supported by bisphosphinimine pincer ligands

248th National Meeting (2014)

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