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Published on: July 30, 2017
Synthesis and Characterization of Bimetallic Copper(I) Complexes Supported by a Hexadentate Naphthyridine-Based
Carlos Martínez-Ceberio1, Francisco José Fernández-de-Córdova1, Pablo Ríos1
1Instituto de Investigaciones Químicas (IIQ), Departamento de química Inorgánica, Universidad de Sevilla, Avenida Américo Vespucio 49, Sevilla, 41092, Spain.
Abstract:
Herein, we report the synthesis, characterization, and binding properties of a new ligand, N,N'-di-tert-butyl-3,7-diaza-1,5(2,7)-1,8-naphthyridinacyclooctaphane (tBuN6), with copper (I), CuI, centers. We demonstrate the flexibility and the ability of tBuN6 to adopt various conformations in solution and when coordinated to CuIcenters. NMR studies exhibit the labile coordination nature of CuI. However, the lability of the complexes is blocked by counterion exchange, which enables the use of less coordinating solvents such as tetrahydrofuran (THF) and avoids using acetonitrile. Thus, the exchange of [BF4]- with tetrakis 3,5-bis(trifluoromethyl)phenyl borate, [B(ArF)4]-, in 1·BF4, [Cu2(MeCN)2(tBuN6)][BF4], generates 1·B(ArF)4, which is stable in THF and reacts under a CO atmosphere to generate a syn,syn bis(carbonyl) complex. This complex is sufficiently stable in solution under CO and Ar atmosphere to be characterized by NMR and IR spectroscopy, the latter revealing two stretching bands for the CO bound to the CuI-centers at 2102 and 2088 cm-1.
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