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The reaction of <jats:bold>1<\/jats:bold> with [AuCl(tht)] (tht=tetrahydrothiophene) afforded 2,6\u2010(Ph<jats:sub>2<\/jats:sub>PAuCl)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>SiMe<jats:sub>3<\/jats:sub> (<jats:bold>2<\/jats:bold>). The subsequent reaction of <jats:bold>2<\/jats:bold> with CsF proceeded with elimination of Me<jats:sub>3<\/jats:sub>SiF and yielded the neutral tetranuclear complex <jats:italic>linear<\/jats:italic>\u2010[Au<jats:sub>4<\/jats:sub>Cl<jats:sub>2<\/jats:sub>(<jats:italic>PCP<\/jats:italic>)<jats:sub>2<\/jats:sub>] (<jats:bold>3<\/jats:bold>) comprising a string\u2010like arrangement of four Au atoms. Upon chloride abstraction from <jats:bold>3<\/jats:bold> with NaBAr<jats:sup>F<\/jats:sup><jats:sub>4<\/jats:sub> (Ar<jats:sup>F<\/jats:sup>=3,5\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>) in the presence of tht, the formation of the dicationic tetranuclear complex <jats:italic>linear<\/jats:italic>\u2010[Au<jats:sub>4<\/jats:sub>(<jats:italic>PCP<\/jats:italic>)<jats:sub>2<\/jats:sub>(tht)<jats:sub>2<\/jats:sub>](BAr<jats:sup>F<\/jats:sup><jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub> (<jats:bold>4<\/jats:bold>) was observed, in which the string\u2010like structural motif is retained. Irradiation of <jats:bold>4<\/jats:bold> with UV light triggered a facile rearrangement in solution giving rise to the dicationic tetranuclear complex <jats:italic>cyclo<\/jats:italic>\u2010[Au<jats:sub>4<\/jats:sub>(<jats:italic>PCP<\/jats:italic>)<jats:sub>2<\/jats:sub>(tht)<jats:sub>2<\/jats:sub>](BAr<jats:sup>F<\/jats:sup><jats:sub>4<\/jats:sub>) (<jats:bold>5<\/jats:bold>), which comprises a rhomboidal motif of four Au atoms. In <jats:bold>3<\/jats:bold>\u2013<jats:bold>5<\/jats:bold>, the Au atoms are associated by a number of significant aurophilic interactions. The atom\u2010economic and selective reaction of <jats:bold>3<\/jats:bold> with HgCl<jats:sub>2<\/jats:sub> yielded the neutral trinuclear bimetallic complex [HgAu<jats:sub>2<\/jats:sub>Cl<jats:sub>3<\/jats:sub>(<jats:italic>PCP<\/jats:italic>)] (<jats:bold>6<\/jats:bold>) comprising significant metallophilic interactions between the Au and Hg atoms. Therefore, <jats:bold>6<\/jats:bold> may be also regarded as a metallopincer complex [ClHg(<jats:italic>AuCAu<\/jats:italic>)] between Hg<jats:sup>II<\/jats:sup> and the anionic tridentate ligand [2,6\u2010(Ph<jats:sub>2<\/jats:sub>PAuCl)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> (<jats:italic>AuCAu<\/jats:italic>)<jats:sup>\u2212<\/jats:sup> containing a central carbanionic binding site and two \u201cgold\u2010arms\u201d contributing pincer\u2010type chelation trough metallophilic interactions. Compounds\u2005<jats:bold>1<\/jats:bold>\u2013<jats:bold>6<\/jats:bold> were characterized experimentally by multinuclear NMR spectroscopy and X\u2010ray crystallography and computationally using a set of real\u2010space bond indicators (RSBIs) derived from electron density (ED) methods including Atoms In Molecules (AIM), the Electron Localizability Indicator (ELI\u2010D) as well as the Non\u2010Covalent Interaction (NCI) Index.<\/jats:p>","DOI":"10.1002\/chem.201904106","type":"journal-article","created":{"date-parts":[[2019,10,4]],"date-time":"2019-10-04T10:13:09Z","timestamp":1570183989000},"page":"275-284","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":30,"title":["Tri\u2010 and Tetranuclear Metal\u2010String Complexes with Metallophilic d<sup>10<\/sup>\u2013d<sup>10<\/sup> 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