ABSTRACT
The title compound, [IrZnI2(C10H15)(C3H9P)2]·0.5C6H6 or [Cp*(PMe3)2Ir]-[ZnI2] (Cp* = cyclo-C5Me5) was obtained and characterized as its benzene solvate [Cp*(PMe3)2Ir]-[ZnI2]·0.5C6H6. The bimetallic complex in this structure contains the Lewis-acidic fragment ZnI2 bonded to the Lewis-basic fragment Cp*(PMe3)2Ir, with an Ir-Zn bond distance of 2.452â (1)â Å. The compound was obtained by reacting [Cp*(PMe3)IrI2] with 2-Ad2Zn (2-Ad = 2-adamant-yl), resulting in the reduction of the IrIII complex and formation of the IrI-ZnII adduct. The crystal studied was a twin by non-merohedry with a refined BASF parameter of 0.223â (1).
ABSTRACT
New routes to 1- and 2-adamantyl anion equivalents are described, starting from commercially available 1- and 2-adamantylzinc bromides and employing reducing metals (Mg; Li). Adamantylmagnesium bromides (both 1-AdMgBr and 2-AdMgBr) can reliably be produced via reaction of the corresponding adamantylzinc bromides with excess magnesium metal. Reactions of adamantylzinc bromides with stoichiometic lithium biphenylide or lithium 2,2'-bipyridylide afford the new diadamantylzinc species, 1-Ad2Zn and 2-Ad2Zn, isolable free of solvent and salt impurities. Addition of 2,2'-bipyridine (bipy) leads to the crystalline adducts 1-Ad2Zn(bipy) and 2-Ad2Zn(bipy), which were structurally characterized. The resulting adamantyl anions were used in order to generate the first adamantyl complexes of mercury (1- and 2-Ad2Hg), gold (1- and 2-AdAu(PPh3), 1- and 2-AdAu(PCy3)) and bismuth (2-Ad2BiBr), of which 1- and 2-Ad2Hg, 2-AdAu(PPh3), 2-AdAu(PCy3), and 2-Ad2BiBr were isolated. These include the first structurally characterized unsupported 2-adamantyl metal complexes.
