6-Diphenylphosphinoacenaphth-5-yl-mercurials as Ligands for d10 Metals. Observation of Closed-Shell Interactions of the Type Hg(11)••M; M = Hg(II), Ag(I), Au(I)

The salt metathesis reaction of ArLi with HgCl2 produced Ar2Hg (1, Ar = 6-Ph2P-Ace-5), which underwent complex formation with d10-configurated transition metal chlorides and triflates to give the complexes 1.HgCl2, 1.Hg(O3SCF3)(2), 1.AgCl, 1.Ag(O3SCF3), [1.Ag(NCMe)(2)](O3SCF3), 1.AuCl, and [1.Au](O3SCF3) comprising significant metallophilic interactions between Hg(II) and Hg(II), Ag(I), and Au(I), respectively. The transmetalation reaction of ArSnBu3 with HgCl2 afforded ArHgCl (2) that also forms a complex with additional HgCl2, namely, 2.HgCl2, which however lacks metallophilic interactions. Compounds 2 and 1.HgCl2 possess the same elemental composition and can be interconverted in solution by choice of the solvent. In the presence of tetrahydrothiophene (tht), the complexes 1.AuCl and [1.Au](O3SCF3) underwent rearrangement into the Au(III) cation [cis-Ar2Au](+) ([3](+), which was isolated as Cl and (O3SCF3)(-) salts) and elemental Hg. The reaction of 1.Hg(O3SCF3)(2) with ArH produced the complex ArHg(ArH)(O3SCF3) (4). The metallophilic interactions are theoretically analyzed by a set of real-space bonding indicators derived from the atoms-in-molecules (AIM) and electron localizability indicator (ELI) space-partitioning schemes.