Accession Number : ADA267717


Title :   Synthesis, Characterization, and Polymerization of New Ferrocene- Fluorene Complexes. A Novel High-Molecular Weight Conjugated Polymer with Pendant Ferrocene Groups


Corporate Author : UTAH STATE UNIV LOGAN DEPT OF CHEMISTRY AND BIOCHEMISTRY


Personal Author(s) : Wright, Michael E ; Cochran, Brooks B


Full Text : https://apps.dtic.mil/dtic/tr/fulltext/u2/a267717.pdf


Report Date : Jan 1992


Pagination or Media Count : 29


Abstract : Ferrocenecarboxaldehyde was successfully condensed with fluorene derivatives to afford a series of new complexes, (eta5-C5H5) Fe(eta5-C5H4CH=(9- fluorenyl)) where fluorenyl = 1A, 2-bromo: 2a, 2,7-dibromo; 3, 2-nitro. The ferrocene-fluorenyl derivatives la and 2a were converted to the monocarboxaldehyde, tributylstannyl, bis(carboxaldehyde), and bis(tributylstannyl) complexes (lb, lc, 2b, and 2c, respectively). Complexes lb and 2b were characterized by single-crystal x-ray molecular structures. The fluorenyl ring systems were tilted out of the eta5-C5H4 plane by 39 deg. Treatment of lc and 2c with I2 afforded the mono- and bis(iodo)fluorenyl complexes ld and 2d, respectively. The reactivity of complexes 2a-d was explored. The alkynylation (alkyne, L2PdCl2, CuI, PPh3) of 2a was an extremely poor reaction giving little or no cross-coupling. Complex 2b did not undergo the Knoevenagel polycondensation with bis(cyanoacetate) comonomers. Treatment of 2c with acid chlorides under Stille cross-coupling conditions afforded ketone product and iodobenzene showed no cross-coupling. Complex 2d did copolymerize very cleanly with 2,5(diethynyl)-1,4-(decoxy)benzene using palladium catalysis to afford a soluble, high-molecular weight conjugated polymer, 4. A model compound, 5, was prepared from cross-coupling ld with 2,5-(diethynyl)-1,4- (decoxy)benzene.


Descriptors :   *COMPLEX COMPOUNDS , *ALDEHYDES , *CARBOXYL RADICALS , *FLUORENES , *FERROCENES , BENZENE , MODELS , POLYMERS , MOLECULAR WEIGHT , SINGLE CRYSTALS , CHEMICAL BONDS , COPPER , CHLORIDES , ACIDS , PALLADIUM , PHENYL RADICALS , RINGS , CATALYSIS , MOLECULAR STRUCTURE , ELECTRON DONORS , MONOMERS , ORGANIC COMPOUNDS , ALKYNES , KETONES , CONDENSATION , IODINE , OXIDATION , X RAYS , REACTIVITIES , POLYMERIZATION , SYNTHESIS , TRANSITION METALS


Subject Categories : Organic Chemistry
      Physical Chemistry
      Polymer Chemistry
      Crystallography


Distribution Statement : APPROVED FOR PUBLIC RELEASE