Insights into non-covalent interactions in dicopper(ii,ii) complexes bearing a naphthyridine scaffold: anion-dictated electrochemistry

Abstract

A family of bis(µ-hydroxido)dicopper(II,II) complexes bearing a naphthyridine-based scaffold has been synthesized and characterized. Cyclic voltammetry reveals that the nature of the anions present in the complexes plays a pivotal...

Copper–oxygen adducts: new trends in characterization and properties towards C–H activation

“…215,217,218 More to this point, De Tovar recently evidenced the tunability of their electrochemical properties through the formation of intimate ion pairs with surrounding anions by non-covalent interactions, highlighting the importance of second sphere effects when designing such [Cu 2 II (m-OH) 2 ] 2+ species. 219 Interestingly and counter-intuitively, Cu II or [Cu 2 II (m-OH)(susan)] 3+ respectively (6-hpa and susan ligands are depicted in Chart 2). In both cases, remarkably high activities compared to phenol oxidation in the ortho position (tyrosinase like activity) were observed (see Section 4.2.1).…”

“…214,216,217 More to this point, De Tovar recently evidenced the tunability of their electrochemical properties through the formation of intimate ion pairs with surrounding anions by non-covalent interactions, highlighting the importance of second sphere effects when designing such [Cu2 II (µ-OH)2] 2+ species. 218 Interestingly and counter intuitively, Cu II Cu III (μ-O)x intermediates could be more efficient for strong C−H bond activation than the corresponding Cu III Cu III (μ-O)x counterparts. In 2013, Yoshizawa and Shiota postulated that HAA activation could preferably occurs after protonation and reduction of a O species, leading to a mixedvalent intermediate.…”

Non-coordinating counteranion as a powerful tool to tune the activity of copper water oxidation catalysts

“…Additionally, the non-covalent interactions between the oxygen element in OTf − and the hydrogen element in the complex tend to promote the activity of C–N bond cleavage. 18…”

“…Despite it has been recognized that non-coordinating counteranions are important for metal complexes in many catalytic processes, 18–20 few studies described the influence of non-coordinating counteranions on the catalytic activity of Cu-WOCs. In this work, we synthesized two types of copper-bipyridine complexes, [(bpyR)Cu]X, with five different counteranions (R = H or CH 3 ; X = OAc − , Cl − , SO 4 2− , NO 3 − , OTf − ) as shown in Scheme 1 and Fig.…”