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Award ID contains: 2044834

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  1. Abstract The conventional synthetic approach to transition metal pincer complexes calls for the preparation of the tridentate pincer (pro)ligand first, with subsequent introduction of the transition metal center as the last step. This work demonstrates that the alternative synthetic logic, where the central main group element is introduced last, can be applicable to a number of PEP pincer complexes (E=B, Al, Si, P) derived from phosphinophenols and phosphinopyrroles. This approach obviates the need to isolate well‐behaved propincer precursors, and instead relies on the formation of phosphine‐metal adducts first, whose nature determines the stoichiometry of the needed main group reagent to complete the synthesis. 
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  2. The synthesis and coordination chemistry of a new class of silyl pincer ligand featuring pyrrole-based linkers is reported. The steric and electronic properties of these bis(phosphinopyrrole)methylsilane ligands were interrogated using their palladium, rhodium, and platinum complexes. The pyrrole-based linker attenuates the donor ability of the ligand relative to its reported 1,2-phenylene congener while maintaining a similar steric profile. Additionally, the silyl donor connected to the N -pyrrolyl groups exhibits a weaker trans influence than the analogous ligand featuring 1,2-phenylene linkers. 
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