[2.2]Paracyclophanediyldiphosphane Complexes of Gold

Abstract

We have prepared digold(I) complexes with the rigid-backbone diphosphane ligands PhanePhos, xyl-PhanePhos, and Ph 2 -GemPhos. All complexes were characterized by singlecrystal X-ray diffraction, NMR, IR, Raman, and photoluminescence (PL) spectroscopy. [PhanePhos(AuCl) 2 ] and [Gem-Phos(AuCl) 2 ] show a very similar ligand scaffold, but different (aurophilic vs. nonaurophilic) intramolecular Au-Au distances. Absorption and PL spectra of both compounds are quite similar. Theoretical investigations reveal that the excited states are of different character (i.e., influenced by the Au-Au contacts). The respective transition energies, however, lie close to each other, thus resulting in similar experi-

Alkynyl-functionalized gold NHC complexes and their coinage metal clusters

“…[17][18][19] This attractive d 10 -d 10 -dispersion interaction, in which the distance between two gold(I) ions is well below the sum of their van der Waals radii, is a special case of metal-metal bonds (metallophilicity), which is also observed for other metals like silver and mercury. [20][21][22] Therefore, multi-and heterometallic gold complexes are being thoroughly investigated for the influence of metallophilic interactions on luminescence 23 , and cooperative effects in certain catalytic steps.…”

Gold(I) Catalysis at Extreme Concentrations Inside Self‐Assembled Nanospheres

“…[16] As expected, the reaction proceeds more slowly than the reaction shown in Table 1, and at room temperature in the presence of 2 mol % A 24 Pd 12 (OTf) 24 (48 mol % AuCl) no conversion was obtained. [18] Upon diluting the local goldchloride concentration within the spheres, by using lower A/B ratios during the sphere formation, the shoulder at about l = 315 nm decreases in intensity ( Figure 6; see Figure S121 in the Supporting Information). Under reaction conditions in which the overall gold concentration was 1.19 10 À4 m (sphere concentration 1.25 10 À6 m) the reaction performed smoothly at 90 8C, leading to 19.3 % conversion and implying a TON of 26 with respect to the gold concentration (see Table S11 in the Supporting Information).…”

Coinage Metal Complexes of Bis‐Alkynyl‐Functionalized N‐Heterocyclic Carbenes: Reactivity, Photophysical Properties, and Quantum Chemical Investigations

“…[11,12] Besides their different steric ande lectronic properties compared to, for example, phosphines, NHCs are easily functionalized, as almosta ny organic substituent can be attached to the nitrogen atoms. [31][32][33][34][35][36][37][38][39][40][41] This also reflects their special ability to form close metal-metalc ontacts, which is commonly known as metallophilicity. Besides their applicationi nc atalysis, coinage metal compounds have also been extensively investigatedw ith respect to their photoluminescence properties.…”

“…In these compounds, two or more gold(I)i ons are located in close proximity to each other and often well below the sum of their van der Waals radii.A si tw as first considered to be au nique property of Au I compounds, this effect was originally called aurophilicity. [35] To wards obtaining ad eeper understanding and uncovering potentiala pplications of these metal-metal interactions, [50][51][52][53] we have studied the properties of polynuclear metalc omplexes with novel polydentate NHC ligands ystems. [47] Because of this kind of metal-metal interaction,p olynuclear coinage metal compounds are intensely investigated in order to gain knowledge about the influence of metallophilic interactions on specific properties.…”