Martínez-Ceberio Carlos, Fernández-de-Córdova Francisco José, Ríos Pablo, Rivada-Wheelaghan Orestes
Instituto de Investigaciones Químicas (IIQ), Departamento de química Inorgánica, Universidad de Sevilla, Avenida Américo Vespucio 49, Sevilla, 41092, Spain.
Inorg Chem. 2025 May 5;64(17):8630-8638. doi: 10.1021/acs.inorgchem.5c00321. Epub 2025 Apr 22.
Herein, we report the synthesis, characterization, and binding properties of a new ligand, ,'-di--butyl-3,7-diaza-1,5(2,7)-1,8-naphthyridinacyclooctaphane (), with copper (I), Cu, centers. We demonstrate the flexibility and the ability of to adopt various conformations in solution and when coordinated to Cucenters. NMR studies exhibit the labile coordination nature of Cu. 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 [BF] with tetrakis 3,5-bis(trifluoromethyl)phenyl borate, [B(Ar)], in , [Cu(MeCN)(N6)][BF], generates , which is stable in THF and reacts under a CO atmosphere to generate a 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 Cu-centers at 2102 and 2088 cm.
在此，我们报道了一种新型配体，即1,1'-二异丁基-3,7-二氮杂-1,5(2,7)-1,8-萘啶环辛八烷（N6）与铜（I）（Cu）中心的合成、表征及配位性质。我们证明了N6在溶液中以及与Cu中心配位时具有采取各种构象的灵活性和能力。核磁共振（NMR）研究表明Cu的配位性质不稳定。然而，通过抗衡离子交换可阻止配合物的不稳定性，这使得能够使用诸如四氢呋喃（THF）等配位性较弱的溶剂，并且避免使用乙腈。因此，在[Cu(MeCN)(N6)][BF4]中，用四[3,5-双（三氟甲基）苯基]硼酸酯[B(ArF)4]交换[BF4]，生成[Cu(THF)(N6)][B(ArF)4]，其在THF中稳定，并且在CO气氛下反应生成一种双（羰基）配合物。该配合物在CO和Ar气氛下在溶液中足够稳定，可通过NMR和红外（IR）光谱进行表征，后者显示在2102和2088 cm-1处有两个与Cu中心配位的CO的伸缩带。
