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.
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