The value of n in Ph(2)P(CH(2))(n)PPh(2) controls whether a simple ring or a [2]catenane is formed in the reaction with a digold(I) diacetylide. Simple macrocyclic gold complexes are obtained for n=2 and the family of organometallic [2]catenanes for n=4 and 5 (see structure); a mixture of these products as well as a third isomer results when n=3.