Experimental and Theoretical Comparison of the Metallophilicity between d~(10)?d~(10) Au~I?Hg~(II) and d~8?d~(10) Au~(III)?Hg~(II) Interactions

摘要

The heteronuclear Au~I/Hg~(II) complexes [Hg{AuR(μ-2-C_6H_4PPh_2)}_2] [R = C_6F_5 (1), C_6Cl_2F_3 (2)] were prepared by reacting [Hg(2-C_6H_4PPh_2)_2] with [AuR(tht)] (1:2) and further transformed into the AuIII/ HgII species [Hg{Au(C_6F_5)Cl_2(μ-2-C_6H_4PPh_2)}_2] [R = C_6F_5 (3), C_6Cl_2F_3 (4)] by the addition of 2 equiv of PhI· Cl_2. The crystal structures of 1?3 display Au···HgII interactions, which in the case of 3 is the first AuIII···Hg contact described to date. Theoretical calculations on model systems of the C_6F_5 derivatives evidence that the attraction between Au~I or Au~(III) and Hg~(II) arise from dispersion-type interactions and that both contacts are of the same strength.