Issue 19, 2017

Adamantyl metal complexes: new routes to adamantyl anions and new transmetallations

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.

Graphical abstract: Adamantyl metal complexes: new routes to adamantyl anions and new transmetallations

Supplementary files

Article information

Article type
Paper
Submitted
03 Feb 2017
Accepted
18 Apr 2017
First published
19 Apr 2017

Dalton Trans., 2017,46, 6212-6217

Adamantyl metal complexes: new routes to adamantyl anions and new transmetallations

D. Armstrong, F. Taullaj, K. Singh, B. Mirabi, A. J. Lough and U. Fekl, Dalton Trans., 2017, 46, 6212 DOI: 10.1039/C7DT00428A

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