Bulky guanidinates for the stabilization of low oxidation state metallacycles

This article summarizes the development of a new class of very bulky guanidinate ligands. These have been used to prepare unprecedented examples of heterocycles containing groups 2, 13, 14 or 15 elements in the +1 oxidation state. The ligands have also been harnessed in the preparation of the only examples of guanidinato, and/or closely related amidinato, complexes of iron(I), cobalt(I) and planar four-coordinate lanthanide(II) metals. Preliminary studies of the further chemistry of these very reactive complexes are also reviewed. Throughout, the tendency of the bulky guanidinate ligands to exhibit ligating and stabilizing properties more akin to those of bulky β-diketiminate ligands than less bulky amidinates or guanidinates, will be discussed.