Abstract
<jats:title>Abstract</jats:title> <jats:p>The coordination environment of central atoms in molecular compounds is a key factor determining bonding, reactivity and properties. To explore the limits of possible coordination modes is possible in two ways: maximizing or minimizing coordination numbers. The former promises enhanced stability due to the saturation of the coordination sphere, while the latter is frequently accompanied high and sometimes unexpected reactivity that may lead to decomposition. Therefore, the stabilization of low‐coordinated environments requires intricate ligand design and sophisticated methods of synthesis, both of which have developed into an art of their own; as commonly, each element requires a distinct approach. The last decade has seen a spectacular development of application of established and newly developed ligand scaffolds that have been applied to many main group elements and enabled the push to the final frontier in low‐coordinate compounds for a wide range of elements: coordination number 1. This review is meant to give an overview with some landmark historic examples and focus on the vivid recent developments.</jats:p>