The first copper(I)-olefin complexes bearing a 1,3,4-oxadiazole core: Alternating-current electrochemical crystallization, X-ray experiment and DFT study

Abstract

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SYNTHESIS, CRYSTAL STRUCTURE, HIRSHFELD SURFACE ANALYSIS AND QUANTUM CHEMICAL CALCULATIONS OF [Cu2(C6H9N3S)2(ClO4)2] π-COMPLEX WITH 2-ALLYLAMINO-5-METHYL-1,3,4-THIADIAZOLE

“…Thus, metal ions connect two Thiaz1 ligands into centrosymmetric [Cu 2 (Thiaz1) 2 (ClO 4 ) 2 ] fragment with one six-member {Cu 2 N 4 } cycle and two six-member {CuN 2 C 3 } rings. Similar centrosymmetric dimers were found previously in the structure of CuNO 3 and Cu(CF 3 SO 3 ) π-complexes with Thiaz1 [9] as well as CuNO 3 and CuClO 4 π-complexes based on 2-allylthio-5-phenyl-1,3,4-oxadiazole ligand [15]. The strength of Cu(I)-(C=C) interaction in 1 is confirmed by the fact that allylic C=C bond is elongated to 1.355(5) Å (compared with a nominal value of 1.33 Å and a value of 1.340(7) Å in Thiaz1 structure itself [5]) due to back-donation from an occupied 3d metal orbital to a low-lying empty π* orbital of the olefin.…”

A “Flexible” Rigid Rod, trans-Pt(PMe3)2(C≡CC6H4CN)2 (L1), to Form 2D [{Cu2(μ2-X)2}2(μ4-L1)]n Polymers (X = Br, I) Exhibiting the Largest Bathochromic Emissions

“…Interestingly both geometries, trans - ( CP1 ) and cis - ( CP2 ) were isolated. Many precedents of the trans -Cu 2 X 2 L 2 L′ 2 motifs exist (X = Cl, Br, or I; L and L′ = (N-donor/η 2 -CC), (L = C – /P-donor), (B-η 2 -CC/P-donor), (η 2 -CC/P-donor), (S-donor/N-donor), (Se-donor/N-donor), (S-donor/P-donor)). Conversely, the cis form is extremely rare and does not exist, unless a bridging ligand forces this type of geometry. , In CP2 , the cis geometry is obtained without the use of a bridging ligand.…”

3-Phenyl-4-(prop-2-en-1-yl)-5-[(prop-2-en-1-yl)sulfanyl]-4H-1,2,4-triazole

“…Due to the π,σ-coordination to copper(I) ions via the η 2 -allyl group and the two heterocyclic N atoms, Atr molecules form compounds based on dimeric building blocks {Cu 2 (Atr) 2 } that are stable both in crystalline form and in solution [18,19]. Such stability in solution (usually in ethanol or acetonitrile) is not characteristic of Cu(I) π-complexes with other allylazoles, such as 1,2,3triazoles, tetrazoles, 1,3,4-thiadiazoles, and 1,3,4-oxadiazoles [20][21][22][23]. Despite the fact that all investigated crystalline copper coordination compounds with Atr were studied by the single-crystal X-ray diffraction method, while Atr itself was characterized only by spectroscopic techniques [19], in the present work, we focused on the structural characterization of 3-phenyl-4-(prop-2-en-1-yl)-5-[(prop-2-en-1-yl)sulfanyl]-4H-1,2,4-triazole (Atr) (Figure 1) by the diffraction technique, accompanied by an energy framework computational study.…”