Metal‐ligand cooperativity (MLC) had a tremendous impact on d‐block metal‐mediated bond activation and homogeneous catalysis. Is this concept translatable to the elements of the p‐block? Are there analogies already at hand? In this review, we describe contributions in which a p‐block element (group 13–15) and its ligand (surrounding molecular framework) operate synergistically in a substrate activation or a catalytic cycle. This activity is termed element‐ligand cooperativity (ELC), in correspondence to MLC. After the concepts of p‐block low‐valent states and frustrated Lewis pairs mimicking the ambiphilic reactivity of transition metals, the spatial proximity of nucleophilic and electrophilic reaction sites and a small HOMO‐LUMO gap in a p‐block ELC complex might offer yet another approach. Selected examples shall illustrate common reactivities of ELC, disclose conceptual analogies with d‐block MLC, and outline shortcomings in this field.

In this work the first examples of C−N bond activation by insertion into the geometrically constrained PIII-centre are shown. The mechanisms of these activation processes leading to new PV species...

An unexpected rearrangement occured when an imidazolinium based OCO pincer-type ligand (1) was reacted with PCl3 producing a chlorophosphine with a pendant oxazolium "arm" (3). The mechanism of this rearrangement...