Revisiting the Bonding Model for Gold(I) Species: The Importance of Pauli Repulsion Revealed in a Gold(I)-Cyclobutadiene Complex.

Understanding the bonding of gold(I) species has been central to the development of gold(I) catalysis. Herein, we present the synthesis and characterization of the first gold(I)-cyclobutadiene complex, accompanied with bonding analysis by state-of-the-art energy decomposition analysis methods. Analysis of possible coordination modes for the new species not only confirms established characteristics of gold(I) bonding, but also suggests that Pauli repulsion is a key yet hitherto overlooked element. Additionally, we obtain a new perspective on gold(I)-bonding by comparison of the gold(I)-cyclobutadiene to congeners stabilized by p-, d-, and f-block metals. Consequently, we refine the gold(I) bonding model, with a delicate interplay of Pauli repulsion and charge transfer as the key driving force for various coordination motifs. Pauli repulsion is similarly determined as a significant interaction in Au I -alkyne species, corroborating this revised understanding of Au I bonding.