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

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.