Rotaxanes Derived from Dimetallic Polyynediyl Complexes:Extended Axles and Expanded Macrocycles.

A new35-membered macrocycle 3bderived from 1,10-phenanthrolineand two 2,9-p-C6H4O(CH2)6O substituents that tether a 2,7-naphthdiyl moietyis synthesized. CuI complexes of 3band a previouslyreported analog in which the naphthdiyl is replaced by a m-C6H4group (3a) are reacted withthe hexatriynyl complex trans-(C6F5)(p-tol3P)2Pt(CC)3H (1.0:2.5 mol ratios) in the presence of K2CO3(4.0–5.0 equiv) and I2(1.3–1.8equiv) in THF at 55 °C. Workups afford the rotaxanes 5·3aand 5·3b(45–23%), in which the macrocyclesare threaded by the sp carbon chain of the diplatinum dodecahexaynediylcomplex trans,trans-(C6F5)(p-tol3P)2Pt(CC)6Pt(Pp-tol3)2(C6F5) (5), which is also obtained as a byproduct.The yields of 5·3aand 5·3baremuch higher than in the case with octatetraynediyl (C8)analogs, and their spectroscopic properties and crystal structuresare analyzed in detail, especially with reference to recent DFT studies. [ABSTRACT FROM AUTHOR]