Syntheses of Beltlike Polycyclodiynes Intercalated with Triosmium Carbonyl Clusters

Abstract

The bis(cyclodiyne) complex Os 3 (CO) 8 (μ 3 -η 2 -C 14 H 20 ) 2 ( 4 ) has been prepared by treating Os 3 (CO) 10 (μ 3 -η 2 -C 14 H 20 ) ( 1 ) with Me 3 NO in the presence of cyclotetradeca-1,8-diyne (C 14 H 20 ) ligand. Thermolysis of 4 leads to the osmacyclopentadiene complex Os 3 (CO) 9 (μ-η 4 -(C 14 H 20 ) 2 ) ( 3 ). The tris(cyclodiyne) complex (Os 3 (CO) 8 ) 2 (μ 3,μ 3 -η 2,η 2 -C 14 H 20 )(μ 3 -η 2 -C 14 H 20 ) 2 ( 5 ) is obtained from the reaction of (Os 3 (CO) 10 ) 2 (μ 3,μ 3 -η 2,η 2 -C 14 H 20 ) ( 2 ) with Me 3 NO and C 14 H 20, while photoirradiation of 2 and C 14 H 20 affords the bis(osmacyclopentadiene) complex (Os 3 (CO) 9 ) 2 (μ,μ-η, 4 η 4 -(C 14 H 20 ) 3 ) ( 6 ). Co-irradiation of 3 and 1 also produces 6 . Compounds 3, 4, 5, and 6 can be viewed as cluster-intercalated, beltlike polycyclodiynes. The structures of 4 and 6 (two isomers) have been determined by an X-ray diffraction study.