Polynuclear aryl derivatives of Group 11 metals. Synthesis, solid state-solution structural relationship, and reactivity with phosphines

Abstract

The synthesis of homoleptic aryl derivatives of group 11 metals has been performed by reacting the monochlorides [CuCl], [AgCl], and [AuCOCl] with MesMgBr (Mes = 2,4,6-Me3C6H2). The resulting products [Cu6Mes5] (1), [Ag4Mes4] (2), and [Au6Mes5]-2THF (3) have been isolated as crystalline thermally stable compounds. They have, in the solid state, cyclic structures whose molecular geometries are discussed within. MW determination by cryoscopy in benzene and NMR spectra in both C6D6 and C6D12 showed that the three oligomeric structures were in equilibrium with the respective dimeric form of the molecule. In each case the dimeric form was the prevailing species in solution. The solution equilibrium was very rapidly established for the silver and gold complexes and was relatively slower for the copper complex. In the case of the copper complex the rate of equilibrium was solvent dependent, being much faster in toluene (tX/2 for CugMesg being ca. 0.66 h) than in cyclohexane (t1/2 being ca. 56 h). The addition of electron-rich arenes to cyclohexane solutions of 1 greatly enhanced the rate of conversion of the pentamer to dimer.

Mixed Tetrahedral Zintl Clusters: Single Crystal Structure Determination of [Si4‐xGex]4−, [(MesCu)2(Si4‐xGex)]4−, and the 29Si MAS NMR Spectra of A4Si2Ge2 (A=K, Rb)

“…MesCu was prepared according to literature procedures. [24] [18]-Crown-6 was sublimated under dynamic vacuum at 80 8C. Liquid ammonia was dried and stored over sodium metal.…”

First Incorporation of the Tetrahedral [Sn4]4- Cluster into a Discrete Solvate Na4[Sn4] (NH3)13 from Solutions of Na4Sn4 in Liquid Ammonia

“…CuMes was prepared according to literature [21]. 18-Crown-6 was sublimed under dynamic vacuum at 80 • C. Liquid ammonia was dried and stored over sodium metal.…”

Optimized palladium catalyst systems for the selective liquid-phase hydrogenation of functionalyzed alkynes

“…This was done by adding 50 ml of a solution of an organocopper compound. Mesityl copper, prepared according to Meyer et al [11], and p-tolyl copper, prepared according to Spee et al [3], were used, kindly provided by A.M. Arink of the Metal-Mediated Synthesis group of Utrecht University. Different amounts of copper were added, up to an amount corresponding to a 1:1 Cu:Pd molar ratio (1.2 wt.% Cu with 2 wt.% Pd).…”