Role of Dispersion in Metallophilic Hg···M Interactions (M = Cu, Ag, Au) within Coinage Metal Complexes of Bis(6-diphenylphosphinoacenaphth-5-yl)mercury

Abstract

The previously reported bis(6-diphenylphosphinoacenaphth-5-yl)mercury (1) was used as ligand for the preparation of the copper(I) complexes, 1·CuCl and [1·Cu(NCMe)]BF, which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. DFT calculations employing topological analysis of the electron and electron pair densities within the AIM and ELI-D space-partitioning schemes revealed significant metallophilic Hg···Cu interactions. Evaluation of noncovalent bonding aspects according to the noncovalent interaction (NCI) index was applied not only for the Cu complexes 1·CuCl and [1·Cu(NCMe)]BF but also for the previously reported Ag and Au complexes, namely, [1·MCl] (M = Ag, Au) and [1·M(NCMe)] (M = Ag, n = 2; M = Au, n = 0), and facilitated the assignment of attractive dispersive Hg···M interactions with the Hg···Cu contacts being comparable to the Hg···Ag but weaker than the Hg···Au interactions. The localization of the attractive noncovalent bonding regions increases in the order Cu < Ag < Au.

Transmetallation of Bis(6‐diphenylphosphinoacenaphth‐5‐yl)‐Mercury and ‐Tributyltin with Precious Metal Chlorides

“…Within the ELI-D framework, the Pd-Cl bonds are assigned as ionic Pd + Clcontacts as no corresponding ELI-D bonding basins are formed. The differences between M-C and M-P bonds are further corroborated by an inspection of the NCI analysis, which reveals red colored donut-shaped areas along the M-P bonds (see Figure 2, [15,16,29] The palladophilic interaction is further validated in the formation of a blue colored disk shaped area along the Pd-Pd axis in the NCI analysis ( Figure 6…”

The Effect of Donor Additives on the Stability and Structure of 5‐Diphenylphosphinoacenaphth‐6‐yllithium

“…5‐Diphenylphosphinoacenaphth‐6‐yllithium, 5‐Ph 2 P‐Ace‐6‐Li, an important starting material for the synthesis of peri ‐substituted scaffolds was isolated for the first time and fully characterized as the tetranuclear (5‐Ph 2 P‐Ace‐6‐Li) 4 · 4toluene and as the dinuclear (5‐Ph 2 P‐Ace‐6‐Li · OEt 2 ) 2 · toluene by X‐ray crystallography and 7 Li MAS and 31 P MAS NMR spectroscopy. Apart from Et 2 O, other donor solvents/additives including THF, DME, TMEDA, DABCO give rise to rapid decomposition of 5‐Ph 2 P‐Ace‐6‐Li.…”

“…Ever since their discovery about 100 years ago, organolithium compounds rank amongst the most versatile and widely used reagents in organic and organometallic chemistry In this regard, 5‐diphenylphosphinoacenaphth‐6‐yllithium, 5‐Ph 2 P‐Ace‐6‐Li (Scheme ), has been extensively used for the preparation of peri ‐substituted acenaphthyl scaffolds to study the through‐space interactions between the P atom and a variety of main group elements (B, Al, Ga, In, Tl, Si,, Sn, Pb, P, As, Sb,, Bi and Te) as well as transition metals (Au,, Hg, ).…”

Trinuclear Gold–Carborane Cluster as a Host Structure

“…Due to the ease of formation for Au and Hg complexes with metallophilic interactions, we also considered the Hg 2+ cation. The optimized structure with Hg 2+ in the centroid is unstable and dissociates (–98 kcal/mol).…”