1D Helical Polymeric Chain with a Pseudo-5₃ Screw Axis Formed by Cuprophilicity. Synthesis and Crystal Structure of Copper(I) Pivalate

Abstract

A coordination polymer, [Cu5(piv)5]n (piv = pivalate), was prepared by a thermal decomposition method. The unit cell of the crystal structure consisted of one right-handed helical chain and one left-handed helical chain, which were formed by an alternation of Cu(I) ions and carboxylate (O-C-O) groups. This chain possessed a pseudo-5(3) screw axis; the second-order structure was suggested to be realized by a balance between the cuprophilicity and a steric effect of the tert-butyl groups.

Copper(I) Acetate: A Structurally Simple but Highly Efficient Dinuclear Catalyst for Copper‐Catalyzed Azide‐Alkyne Cycloaddition

“…Encouraged by the results from Cat-1, other structurally well-defined copper(I) benzoate, [19] copper(I) trifluoroacetate [20] and copper(I) pivalate [21] samples were tested under the same conditions (see: entry 7 in Table 1). As shown in Figure 2, each of them represents an amazing polynuclear Cu(I) complex or polynuclear Cu(I) complex polymer, in which the carboxylic acid anions serve as bidentate ligands for Cu(I) ions.…”

Breaking Infinite CuI Carboxylate Helix Held by Cuprophilicity into Discrete Cun Fragments (n = 6, 4, 2)

“…Materials of such type are expected to exhibit a wide range of potential applications in the fields of supramolecular chemistry, [12] asymmetric catalysis, [13] and nonlinear optics. [14] Although discrete copper(I) double-helices supported by oligopyridine and oligophenanthroline ligands are known, [15] complex 2 reported by Awaga [8] and complex 1 prepared in our laboratory are the only copper(I) carboxylates with the infinite helical architectures. A few other extended copper(I) chains and infinite arrays held by cuprophilicity should be mentioned here.…”

“…The synthetic routes toward copper(I) carboxylate complexes have been well developed, [3] but the ease of disproportionation, hydrolysis, and oxidation of these compounds in solutions [4] thwarted the isolation of single crystalline products and the study of their physical and chemical properties. Thus, crystallographic characterization of copper(I) carboxylates has been so far limited to [Cu 2 [8] (e). We have recently expanded the copper(I) carboxylate family with the goal of examining the influence of bridging carboxylate ligands on the solid-state structure of the resulting complexes.…”

“…Thus, the known structural types of copper(I) carboxylates range from discrete [6,10,11] to infinite motifs, [5,[7][8][9] based on mono-, [8] di-, [5,9] tetra-, [6,7,10] or hexanuclear [11] copper(I) units. Such structural diversity is fascinating but not well rationalized so far.…”

“…Its formation was explained by a delicate balance between the cuprophilicity and the steric effect of the bulky tBu groups. [8] Then, one might speculate that the cuprophilicity could be enhanced when bulky but more electrophilic carboxylates than pivalates are employed. However, the use of 2,6-bis(trifluoromethyl)benzoate has afforded an extended polymeric product structurally similar to that of copper(I) acetate.…”