This thesis describes the preparation and characterization of a variety of methyl-, trimethylsilyl-, and diphenylphosphino-substituted indenes. The indenes were then used in the preparation of bis(indenyl)iron(II) complexes. The bis(indenyl)iron(II) complexes were characterized by ¹H, ¹³C, and ³¹P-NMR, UV/visible spectroscopy, cyclic voltammetry, and mass spectrometry. The cyclic voltammetry shows an approximately linear relationship between the oxidation potential and the type of substituent and its ring position, but with increasing substitution leads to lower than expected oxidation potentials. The UV/visible spectra show two absorption bands in the visible region. The position of the bands are essentially unaffected by methyl-substitution, but the low energy band red-shifts with trimethylsilyl- and diphenylphosphino-substitution. Di(2-methylindenyl)iron(II), bis(4,7-dimethyl-indenyl)iron(II), bis(1,3-bis(trimethylsilyl)indenyl)iron(II), rac-bis(1-diphenyl-phosphinoindenyl)iron(II), rac-bis(1-diphenylphosphino-3-methylindenyl)iron(II), and rac-bis(1-diphenylphosphino-2,3-dimethylindenyl)iron(II) were characterized by X-ray crystallography.The planar chiral ferrocenylphosphine bis(1-diphenylphosphinoindenyl)iron(II) is observed to undergo a facile ring-flipping isomerization from the meso isomer to the racemic isomer in THF at ambient temperature. The isomerization is slowed by the addition of the noncoordinating solvent chloroform, but is accelerated by the addition of LiCl. Rate and activation parameters for the isomerization have been determined to be: kobs = 1.6 x 10⁻⁵ s⁻¹ at 23 ℃, ΔH‡ = 58 ± 4 kJ mol⁻¹, ΔS‡ = −140 ± 15 J mol⁻¹ K⁻¹. Deuterium labeling of bis(1-diphenylphosphinoindenyl)iron(II) in the 3- and 3ʹ-position ruled out the isomerization proceeding by [1,5]-proton shifts or dissociative mechanisms. The proposed mechanism for the isomerization proceeds via coordination of two THF ligands with ring-slippage of one of the indenyl ligands until it is coordinated through the phosphine. Coordination of the indenyl ligand by the other face leads to the formation of the other isomer.The heterobimetallic complexes (bis(1-diphenylphosphinoindenyl)iron(II))-cis-dichloropalladium(II), (bis(1-diphenylphosphinoindenyl)iron(II))-cis-dichloro-platinum(II), and [(cyclooctadiene)(rac-bis(1-diphenylphosphinoindenyl)iron(II))-rhodium(I)] tetraphenylborate were prepared. Attempts to prepare dichloro(bis(1-diphenylphosphinoindenyl)iron(II))nickel(II) lead to the formation of trans-dichloro(bis(1-diphenylphosphinoindene))nickel(II). The complex (bis(1-diphenyl-phosphinoindenyl)iron(II))-cis-dichloropalladium(II) is able to catalyze the cross-coupling of bromobenzene with n-/sec-butylmagnesium chloride. However. the reaction is not selective with isomerization of the alkyl group and reduction of the halide occurring via a β-hydride elimination mechanism.
| Identifer | oai:union.ndltd.org:canterbury.ac.nz/oai:ir.canterbury.ac.nz:10092/1266 |
| Date | January 2005 |
| Creators | Fern, Glen Matthew |
| Publisher | University of Canterbury. Chemistry |
| Source Sets | University of Canterbury |
| Language | English |
| Detected Language | English |
| Type | Electronic thesis or dissertation, Text |
| Rights | http://library.canterbury.ac.nz/thesis/etheses_copyright.shtml Copyright Glen Matthew Fern |
| Relation | NZCU |
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