Adamantyl metal complexes: new routes to adamantyl anions and new transmetallations. Issue 19 (26th April 2017)

• Record Type: Journal Article
• Authors: Armstrong, David; Taullaj, Fioralba; Singh, Kamalpreet; Mirabi, Bijan; Lough, Alan J.; Fekl, Ulrich
• Is Part Of: Dalton transactions. Volume 46:Issue 19(2017)
• Page Start: 6212
• Page End: 6217
• Publication Date: 2017-04-26
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt00428a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : We report new approaches to carbanionic metal adamantyls, along with successful transmetallations onto bismuth, gold, and mercury. 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-Ad2 Zn and 2-Ad2 Zn, isolable free of solvent and salt impurities. Addition of 2, 2′-bipyridine (bipy) leads to the crystalline adducts 1-Ad2 Zn(bipy) and 2-Ad2 Zn(bipy), which were structurally characterized. The resulting adamantyl anions were used in order to generate the first adamantyl complexes of mercury (1- and 2-Ad2 Hg), gold (1- and 2-AdAu(PPh3 ), 1- and 2-AdAu(PCy3 )) and bismuth (2-Ad2 BiBr), of which 1- and 2-Ad2 Hg, 2-AdAu(PPh3 ), 2-AdAu(PCy3 ), and 2-Ad2 BiBr were isolated. These include the first structurally characterized unsupported 2-adamantyl metal complexes.