In our efforts to develop new bifunctional base-metal catalysts, we have been investigating sterically svelte tridentate ligands with a combination of ‘hard’ nitrogen and ‘soft’ sulfur donors.[1,2] Our easily prepared SNS ligands and their corresponding metal complexes allow for a comparison of thiolate and amido first-coordination-sphere bases in bifunctional catalysis. Recent results include C-S bond activation to form two new CNS pincer-ligated Fe complexes[3; Fig. 1A] and sterically forcing Cu-NHC complexes to employ ligand assistance in their efficient carbonyl hydrosilylation catalysis.[4; Fig. 1B] Included in this presentation are details of the cross-coupling reactivity of a mixed-valent dinuclear Ni(I,II) SNS complex vs. those of a monovalent Ni(N<sub>2</sub>S<sub>2</sub>) complex.

Good times with simple ligands: Base-metal thiolate and -amido catalysts featuring hemilabile SNS ligands

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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