Directing the Crystal Packing in Triphenylphosphine Gold(I) Thiolates by Ligand Fluorination

Abstract

3 . We use for this purpose (i) DFT electronic structure calculations and (ii) the quantum theory of atoms in molecules and the noncovalent interactions index methods of wave function analyses. Our combined experimental and computational approach yields a general understanding of the effects of ligand fluorination in the crystalline self-assembly of the examined systems, in particular, about the relative force of aurophilic contacts compared with other supramolecular interactions. We expect this information to be useful in the design of materials based on gold coordination compounds.

The Covalent AuI–AuI Bond in (AuF)n (n = 2∼4): A Perspective to Understand the Closed-Shell AuI···AuI Interaction

“…Moreover, there are mysterious but widespread closed-shell metal–metal (M–M) interactions, such as the strong attractions between linearly two-coordinate gold atoms in the +1 oxidation state (Au I ) in molecular gold compounds. , Au I is a closed-shell species with a 5d 10 electronic configuration, with no space for the formation of the covalent Au I ···Au I bond. These unusual Au I ···Au I strong closed-shell interactions attract significant attention in gold chemistry. − In such systems, the observed Au I ···Au I equilibrium distances ( R ) are in the range ca. 2.50–3.50 Å, well below the van der Waals distance (3.80 Å), and often below the nearest-neighbored distance in cubic close-packed gold metal (2.89 Å).…”

Signature of Au as a Halogen

“…In Au 2 F n clusters, the Laplacian at BCPs indicates ionic interaction between Au and F and polar (weak ionic but no covalent) interaction between Au and Au; however, the interactions between closed-shell metal atoms are mysterious, , so a detailed analysis is required to understand the Au–Au interaction in such a system. As Au + is a closed-shell species with a 5d 10 electronic configuration, there has been significant interest in understanding the interaction between Au and Au in gold chemistry. − Due to the strong relativistic effects and dispersion type electron correlations, aurophilic interactions arise, which are intermediate between van der Waals forces and covalent bonding. This dominates the structural chemistry of the system containing Au atoms. − A detailed analysis of the bonding interaction between Au and Au and between Au and F in Au 2 F 2 is presented by Yu et al Our NPA charge analysis, Au–Au and Au–F bond lengths, Mayer bond order analysis, and electron localization function (Figure a) are consistent with the analysis done by Yu et al A similar conclusion can be drawn by analyzing the nature of the NPA charges and the ELF (Figure b) for the Au–Au bond in AuF 2 .…”

Structural Diversity and Argentophilic Interactions in Small Phosphine Silver(I) Thiolate Clusters

“…The argentophilic contact in 3 presents a bcp, the value of ρ ( r bcp ) is 0.029 a. u. and the DI(Ag|Ag) is 0.25 a. u. These values indicate a strong interaction, comparable to aurophilic contacts in phosphino thiolate derivatives [30] and hydrogen bonds in water clusters [65] . The argentophilic contact in 3 is characterized by the values ∇ 2 ρ ( r bcp )=0.0608, | V bcp |/ G bcp =1.24, and G bcp / ρ ( r bcp )=0.68, which along with the negative sign of the total energy indicate a closed shell interaction with a definite covalent character (Table S3) [55,60] .…”

“…Silver thiolate oligomers have a marked tendency to establish coordinative Ag−S bonds and Ag⋅⋅⋅Ag, argentophilic contacts [26] . While the nature and strength of the analogous aurophilic (Au⋅⋅⋅Au) interactions [27] have been extensively studied and their importance in the self‐assembly of gold‐based molecular and cluster materials has been proved, [28–34] the strength and nature of argentophilic interactions is much less explored [26,35–37] . In general, the occurrence of argentophilic interactions is mostly proposed over the base of van der Waals distances [38–41] .…”