FERROCENYL-SUBSTITUDED AND ETHYNYL-SUBSTITUTED FLUORENES VIA ADDITION-ELIMINATION REACTIONS AND 2-ELECTRON REDUCTIONS FROM FLUORENONE - SYNTHESES OF HETERODINUCLEAR ACETYLENE AND FLUORENYL COMPLEXES

Addition of lithioferrocene, ferrocenylacetylide, and unsubstituted acetylides to fluorenone leads to the corresponding 9-fluorenols. Subsequent protonation-dehydration with etheral tetrafluoroboric acid to 9-carbocations, followed by various two-electron reductions, was examined. Also the influence and reaction behavior of hexacarbonyldicobalt-protected acetylene substituents was investigated. The terminal complexes show reeliminations different from those of the bridging analogs. The isolated new compounds 1-14, 9-ferrocenylfluoren-9-ol (1), 9-ferrocenylfluorenium tetrafluoroborate (2), 9-ferrocenylfluorene (3), (eta5-9-ferrocenylfluorenyl)(eta5-pentamethylcyclopentadienyl)ruthenium(II) (4), 9-(ferrocenylethynyl)fluoren-9-ol (5), 9-(ferrocenylethynyl)fluoren-9-ol-hexacarbonyldicobalt complex (6),9-(ferrocenylethynyl)fluorenium tetrafluoroborate-hexacarbonyldicobalt complex (7), 9-(ferrocenylethynyl)fluorene (8a), 1-ferrocenyl-2-(9-fluorenylidene)ethene (8b), 9-(ferrocenylethynyl)fluorenium tetrafluoroborate (9), dimer of 9-(ferrocenylethynyl)fluorene (10), 9-hydroxy-9-ethynylfluorene-hexacarbonyldicobalt complex (11), bis(9-fluoreniumyl)ethyne ditetrafluoroborate (12), bis(9-hydroxyfluoren-9-yl)-ethyne-hexacarbonyldiocobalt complex (13), and bis(9-fluoreniumyl)ethyne ditetrafluoroborate-hexacarbonyldicobalt complex (14), were characterized by MS, IR, NMR, and elemental analysis.