Research on Synthesis, Structure, and Catalytic Performance of Tetranuclear Copper(I) Clusters Supported by 2-Mercaptobenz-zole-Type Ligands

Tetrahedral copper(I) clusters [Cu4(MBIZ)4(PPh3)2] (2), [Cu4(MBOZ)4(PPh3)4] (6) (MBIZ = 2-mercaptobenzimidazole, MBOZ = 2-mercaptobenzoxazole) were prepared by regulation of the copper-thiolate clusters [Cu6(MBIZ)6] (1) and [Cu8(MBOZ)8I]− (5) with PPh3. With the presence of iodide anion, the regulation provided the iodide-containing clusters [CuI4(MBIZ)3(PPh3)3I] (3) and [CuI4(MBOZ)3(PPh3)3I] (7). The cyclic voltammogram of 3 in MeCN (0.1 M nBu4NPF6, 298 K) at a scan rate of 100 mV s−1 shows two oxidation processes at Epa = +0.11 and +0.45 V with return waves observed at Epc = +0.25 V (vs. Fc+/Fc). Complex 3 has a higher capability to lose and gain electrons in the redox processes than complexes 2, 4, 4′, 6, and 7. Its thermal stability was confirmed by thermogravimetric analysis. The catalytic performance of 3 was demonstrated by the catalytic transformation of iodobenzenes to benzonitriles using AIBN as the cyanide source. The nitrile products show potential applications in the preparation of 1,3,5-triazine compounds for organic fluorescence materials.