Cuprophilic Interactions in and between Molecular Entities

Abstract

Despite being weak attractive forces, closed‐shell metallophilic interactions play important roles in the Group 11 metal complexes on their diverse structural and physical features. A plethora of experimental and computational studies has thus been dedicated to such weak attractive d10–d10 interactions, particularly aurophilic and argentophilic interactions. Although d10–d10 CuI–CuI forces had been recognized for four decades, cuprophilic interactions are less explored and they are best evidenced by single‐crystal X‐ray crystallographic analysis on CuI complexes and aggregates thereof, by which precise information about the Cu⋅⋅⋅Cu contacts, shorter than the sum of two van der Waals radii (3.92 Å) between the copper centers concerned can be obtained. Based on recently compelling experimental and spectroscopic evidence for intra‐ and intermolecular cuprophilic interactions in copper chemistry, the present Minireview summarizes recent progress in the past three decades in the synthesis and structures of multinuclear homometallic copper complexes, whereby supported and unsupported d10–d10 CuI–CuI interactions are at work.

A Comparative Experimental and Computational Study of Heterometallic Fe‐M (M = Cu, Ag, Au) Carbonyl Clusters Containing N‐Heterocyclic Carbene Ligands

“…In contrast, in the presence of the bulkier IPr ligand, M ··· M contacts are essentially non‐bonding. This gives further support to the conclusion that metallophilic interactions are rather soft and strongly depends on the steric properties of the ancillary ligands employed in such complexes …”

“…Heterometallic complexes and clusters containing coinage metals in the +1 oxidation state were very attractive since they presented heterometallic bonds and metallophilic interactions, that is, attractive interactions between the closed shell d 10 centres Aurophilicity was investigated at first, in relation also to relativistic phenomena, followed by argentophilicity and cuprophilicity , . Several homoleptic and heteroleptic carbonyl clusters containing 2–8 coinage metals (also mixed ones) supported by Fe, Co, Mo, V and Ru carbonyl moieties were reported , , .…”

Isomerism and dynamic behavior of bridging phosphaalkynes bound to a dicopper complex

“…8); bonding to the bridging alkyne is dominated by the in-phase orbitals. 50,51 As the donation contributions involve the butyne p orbitals and the Cu 4s orbitals, the magnitude of the bonding interaction between the butyne fragment and the dicopper core should not depend on the tilt of the alkyne fragment. Conversely, the orbital interactions for back-donation are highly directional due to involvement of p* and 3d orbitals.…”

Hydrogen and Halogen Bond Mediated Coordination Polymers of Chloro-Substituted Pyrazin-2-Amine Copper(I) Bromide Complexes

“…The structural diversification stems from the very nature of the ligand coordination modes and the tendency of copper halides to form clusters via µ 2 -and µ 3 -halide bridges [73]. In our eight complexes, we obtained three topologies exclusively, namely staircase polymer [74], ranging from 2.7547(13) to 3.086(4) Å, but will not be discussed further in the text.…”