Electrochemical Synthesis and Structural Characterization of a Novel Mixed-valence Copper (I)-copper (II) Complex: {[Bis(ethylenediamine) Copper (II)] Bis[diiodocuprate (I)]}

Abstract

A novel, mixed-valent copper(I)-copper(II) complex, {[bis(ethylenediamine)copper(II)] bis[diiodocuprate(I)]} (1), has been prepared by electrochemical dissolution of a sacrificial copper anode in a solution of ethylenediamine (en), I 2 and tetraethylammoniumperchlorate (TEAP) as supporting electrolyte in acetonitrile (AcN) and characterized by single-crystal X-ray structure determination. The crystal structure of the complex 1 shows that it consists of a CuI 2 polymer formed from I -ligands bridging Cu(I) ions, with a nearly square planar geometry of bivalente Cu(II) atoms chelated by two ethylenediamine ligands. The results also show that direct electrosynthesis of the complex had high current efficiency, purity and electrolysis yield.

Monocopper model of CuB site of pMMO in N4‐environment oxidizes C−H bonds

“…The value of the anodic peak potential coincides with that of freshly prepared [n-Bu 4 N][CuCl 2 ] [22] at E a = 0.20 V (Figures 3 and S17-S20), and to that of the Cu I center in related [Cu(en) 2 ][CuI 2 ] 2 . [23] The second redox process was assigned to [Cu(N4)] + at E a = À 0.22 V, which is close to the anodic peak of the cupric analogue [Cu(N4)(ClO 4 )]ClO 4 at E a = À 0.18 V, thus evidencing their closely related coordination environments (Figures S21-S23). CV of the latter complex displays a reversible copper-centered process at E 1/2 = À 0.20 V vs Fc + /Fc (0.43 V vs NHE) [21] for the couple [Cu(N4)(ClO 4 )] + /[Cu(N4)(ClO 4 )], Figure 3.…”

Toward a Rational Design of 3d-4f Heterometallic Coordination Polymers based on Mixed Valence Copper Centers

“…Another interesting feature in the compound reported by Luo et al is the presence of Cu I centers in the linear CuO 2 and CuN 2 environment, similar to that of 1 and 2 . Linear conformations are common in other d 10 coordination polymers such as Au I , and Ag I ; , however, Cu I is usually reported presenting trigonal , and tetrahedral , geometries, while Cu I /Cu II and Cu I CPs containing linear Cu I are more scarce . On the other hand, according to the Robin and Day classification, 1 and 2 can be described as Class I mixed valence compounds, since in both structures the Cu I and Cu II cations can be identified by the difference in their coordination geometries. , …”

“…48 Another interesting feature in the compound reported by Luo et al is the presence of Cu I centers in the linear CuO 2 and CuN 2 environment, similar to that of 1 and 2. Linear conformations are common in other d 10 coordination polymers such as Au I49,50 and Ag I ; 51,52 however, Cu I is usually reported presenting trigonal 53,54 and tetrahedral 55,56 geometries, while Cu I /Cu II and Cu I CPs containing linear Cu I are more scarce. 57 On the other hand, according to the Robin and Day classification, 1 and 2 can be described as Class I mixed valence compounds, since in both structures the Cu I and Cu II cations can be identified by the difference in their coordination geometries.…”

A rare polyniobotungstate-based framework and its structural transformation in a single-crystal-to-single-crystal process induced by iodide ions

“…3b). 24 Obviously, the structural feature of the coexisting Cu 2+ and Cu + ions in 1 provides the possibility to undergo the structural transformation. The phase purity of the obtained claybank crystals of 2 was confirmed by the PXRD pattern in comparison with the simulated single-crystal data of 2 (Fig.…”