Synthesis, structural and photophysical properties of dimethylphosphino(perfluoro-)phenylene-based gold(i) dimers

Abstract

Starting with 1,2 dibromobenzene and 1,2,3,4 tetrafluorobenzene, dimethyl(2-(trimethylstannyl)phenyl)phosphane, Me2P(o-C6H4)SnMe2, and dimethyl-[2,3,4,5-tetrafluoro 6 (trimethylstannyl)phenyl]phosphane, Me3P(o-C6F4)SnMe3, were synthesized and used in tin-gold exchange reactions to prepare two gold(I) dimers, bis[(2 dimethylphosphino)phenyl]di-gold(I), [Au2(μ2-C6H4PMe2)2],...

Aggregation of Copper(I) and Silver(I) Chloride Phosphane Complexes Determined by Aryl‐Stacking and Weak Hydrogen Bonds in the Ligand Periphery

“…All NMR spectroscopic data were in good agreement with those previously reported [18] . We recently published the synthesis of dimethyl(2,3,4,5‐tetrafluorophenyl)phosphane ( 2 ) [11] . Phosphanes 1 and 2 were used to generate the copper(I) and silver(I) chloride complexes 3 and 4 in tetrahydrofuran by reaction with the respective metal(I) chlorides.…”

“…[18] We recently published the synthesis of dimethyl(2,3,4,5-tet-rafluorophenyl)phosphane (2). [11] Phosphanes 1 and 2 were used to generate the copper(I) and silver(I) chloride complexes 3 and 4 in tetrahydrofuran by reaction with the respective metal(I) chlorides. In each case, the isolated complex always contained a ratio of two phosphanes to one metal chloride units, regardless of the employed equivalence ratio.…”

“…Although intermolecular stacking interactions between the 2,7-diazapyrene ligands are present, they are not as common as in the silver complex and thus do not have an structure-defining impact on the overall aggregation motif. [10] Since we recently studied stacking interactions with regards to their strength and capability to influence structural motifs extensively, [11,12] we now wanted to use aryl•••aryl stacking interactions to influence the aggregation and crystallization behavior of copper(I) and silver(I) chloride complexes [(o-C 6 F 4 R)Me 2 P] 2 MCl (M = Cu, Ag; R = H, F). In addition to the investigations on the aggregation motifs in the solid-state by the means of X-ray diffraction experiments, variable-temperature diffusion-ordered NMR spectroscopy (VT-DOSY) experiments provide further understanding of the aggregation process in solution.…”

Diphenyl‐ and Dimesityl‐Phosphanyl‐Substituted 3,3,4,4,5,5‐Hexafluorocyclopentenyl‐Gold(I) Dimers – Syntheses and Solid‐State Structures

“…We concluded that the fluorination has no major impact on the intramolecular Au⋅⋅⋅Au interaction distance, but strongly predetermines the intermolecular aggregation in the solid‐state. The hydrogen substituted gold(I) dimer aggregates chainlike with intermolecular Au⋅⋅⋅Au contacts, while the fluorine substituted gold(I) dimer shows no additional intermolecular Au⋅⋅⋅Au contacts, but stacking interactions between the perfluorophenylene groups [8] …”

“…The hydrogen substituted gold(I) dimer aggregates chainlike with intermolecular Au•••Au contacts, while the fluorine substituted gold(I) dimer shows no additional intermolecular Au•••Au contacts, but stacking interactions between the perfluorophenylene groups. [8] In this work we wanted to investigate the phenyl-and mesitylphosphane-substituted gold(I) dimers based on the 3,3,4,4,5,5-hexafluorocyclopentene framework, [F 6 cyp(PR 2 )Au] 2 (R = Ph, Mes), and their precursor molecules regarding the different steric demand of the phosphane donor function and the effect on the solid-state structures. The hexafluorocyclopentene (F 6 cyp) framework was used to avoid additional intermolecular aryl-aryl stacking interactions between the ligands like in the case of [Au 2 (μ-2-C 6 F 4 PMe 2 ) 2 ].…”