Synthesis, Characterization, and Polymerization of New Ferrocene- Fluorene Complexes. A Novel High-Molecular Weight Conjugated Polymer with Pendant Ferrocene Groups
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.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1992
- Accession Number
- ADA267717
Entities
People
- Brooks B. Cochran
- Michael E. Wright
Organizations
- Utah State University