Jesús Campos

Tetranuclear cores (M−E) 2 of transition metals (M) and tetrylenes (E II =Si, Ge, Sn) are key motifs in homogeneous and heterogeneous catalysis. They exhibit a continuum of M−M and E−E bonding within the inorganic core that leads to a variety of structures for which there are no specific synthetic methods. Herein, we report a series of highly reduced [Ni 0 Ge II ] 2 squares solely stabilized by bulky terphenyl (C 6 H 3 −2,6‐Ar 2 ) ligands, for which we provide complementary and high‐yielding syntheses. Reactivity studies with common Lewis bases (carbene and CO) evince that the structure of the (M−E) 2 core can be transformed. We have investigated this core modification by computational means, offering a rationale to better understand the continuum of bonding across these clusters.