PREPARATION OF OLIGOMERS CONTAINING TETRAPHENYLSILOLE, ACETYLENE AND AROMATIC-GROUPS IN THE MAIN-CHAIN, AND INCORPORATION OF IRON CARBONYL

Polycarbosilanes with the structure [-SiR2-C=C-Z-C=C]n (R2Si = 2,3,4,5-tetraphenyl-1-sila-2,4-cyclopentadiene; Z = 1,4-benzene, 4,4'-biphenyl, 9,10-anthracene, 2,7-fluorene, 2,5- and 2,6-pyridine, 6,6'-bipyridine, 2.5-thiophene. 2,6-p-dimethylaminonitrobenzene 2,6-p-nitroaniline, 2,6-p-nitrophenol, and 2,7-fluoren-9-one) were prepared by reaction of 1,1-diethynyl-2,3,4,5-tetraphenyl-1-sila-2,4-cyclopentadiene with the appropriate (hetero)aromatic dibromide or diiodide in the presence of [(PPh3)2PdCl2] and CuI. Exo- and endotherms observed in the initial DSC scans were absent in repeat scans. The oligomer where Z = p-C6H4 reacted with [Fe(CO)5] under UV irradiation to give an oligomer containing iron carbonyl fragments attached to ca. 30% of the silole groups.