Synthesis and Characterization of Copper(I) Halide Complexes with N‐(2, 6‐Diisopropylphenyl)‐N′‐benzoylthiourea: Monomeric, Dimeric, and Cage Structures

Abstract

Abstract. The N-(2,6-diisopropylphenyl)-NЈ-benzoylthiourea ligand (shown as L) (1) was synthesized and characterized. Reactions of 1 with CuCl 2 and CuBr 2 afforded the monomeric L 2 CuCl (2) and dimeric [LBrCu(μ-L)] 2 (3), respectively, due to the reduction of Cu II . The reaction of 1 and CuCl gave the same product L 2 CuCl (2), while the treatment of 1 with CuBr led to the formation of a rare example

Discotic Liquid Crystals Based on Cu(I) Complexes with Benzoylthiourea Derivatives Containing a Perfluoroalkyl Chain

“…ese chemical shift changes are attributed to the copper(I) complexes formation, and similar results were found for related three-coordinate copper(I) complexes [33][34][35]. Intramolecular hydrogen-bonding between the coordinated halide ions and NH group was evidenced by X-ray structural analysis for several related complexes [37][38][39].…”

“…e reaction between copper(II) salts and, more generally, the versatile acylthiourea compounds leads to a variety of copper(I) complexes, including tetra-and threecoordinate mononuclear complexes, halide-bridged dinuclear complexes, or cluster-type polynuclear complexes, depending on the halide type and reaction conditions [33][34][35][36][37][38][39]. e complexity of the redox reaction between the copper(II) salts and thiourea compounds results from the combination between the versatility of the acylthiourea ligands and the coordination flexibility of the copper(I) ion.…”

Self‐Assembly of Discrete Copper(I)‐Halide Complexes with Diacylthioureas

“…No comparable example of 4 was found in the literature, where neutral diacylthiourea ligands operate as building block for an empty metallamacrocycle. Previously we have reported on a Cu I chloride complex (H 2 L) 2 CuCl supported by the bulky mono‐acylthiourea [H 2 L = PhC(O)NHC(S)NHAr], whose molecule exhibited a butterfly‐like structure (Figure S8, Supporting Information). In comparison, the S–Cu–S bond angle of 4 [102.4(3)°] is much more acute than that in (H 2 L) 2 CuCl [115.71(2)°], indicating the structural constrain imposed by the formed macrocycle.…”

“…Previously we have reported on a Cu I chloride complex (H 2 L) 2 CuCl supported by the bulky mono‐acylthiourea [H 2 L = PhC(O)NHC(S)NHAr], whose molecule exhibited a butterfly‐like structure (Figure S8, Supporting Information). In comparison, the S–Cu–S bond angle of 4 [102.4(3)°] is much more acute than that in (H 2 L) 2 CuCl [115.71(2)°], indicating the structural constrain imposed by the formed macrocycle. In the crystal structure the neighboring molecules of 4 are connected through a pair of N–H ··· O intermolecular hydrogen bonds resulting in a chain‐of‐rings (Figure S9, Supporting Information).…”

“…In contrast, the investigation of coordination complexes with the diacylthiourea H 4 L is largely unexplored. When considering the performance of the mono‐acylthiourea H 2 L,, the bipodal H 4 L can be expected to bring abundant structural variety in the complexation with Cu X ( X = Cl, Br, I). The two sulfur and the involved halides could play an alternative role in terminal or bridging positions.…”