Structure and reactivity of copper (Ⅰ) oligomers

摘要

The reactivity of oligomeric copper(Ⅰ) complexes towards test elec-trophiles and hydrogen have been studied. The complexes exhibit similar reactivity patterns in most cases. Photochemical irradiation of the tetramer 4, led to the isolation of the ligand 8,2,6-dimethylphenyl-N-phenylthionocarbamate, present in the tetramer. This compound crystallized in the monoclinic system in the P2_1 space group with a = 11.992(5) A, b = 9.886(3) A, c= 12.783(6) A, β = 115.91 (4)°, V = 1360.37(4) A~3, z = 4. The comparison of the structure of the ligand with the tetramer shows the differences in the structure brought about by coordination. A comparison of the structures of the tetramer 4 and the hexamer 5 brings out the differences in the nature of bridging sulphide which considerably alters the properties of the complexes. Differences in the reactivity can be understood in terms of the type of the sulphide bridge present in the complexes. Similarities in the reactivity trends are the result of the dissociation of the oligomers in solution. ~1HNMR studies reveal that the structures of these complexes in the solution state are different from the solid state and account for the similarities in the reactivity patternsof these complexes.