Synthesis of thio and mixed donor atom macrocycles containing coordinated diyne units

Abstract

The acid-catalysed reaction of the diyne complex [{Co₂(CO)₆}₂(μ-η²:μ-η²-HOCH₂C₂C₂CH₂OH)] with a range of dithiols leads in each case to the formation of at least two cyclic products, a monomeric product [{Co₂(CO)₆}₂(μ-η²:μ-η²-SCH₂C₂CCCH₂SR)] and a dimeric product [{Co₂(CO)₆}₂(μ:η²:μ:η²-SCH₂C₂C₂CH₂SR)]₂, [R = (CH₂)_n (n = 3–6)]. This method may also be applied to dithiols that contain additional donor atoms such as S or O to give crown type macrocycles. The crystal structures of several of the above new complexes are reported.