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.

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.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1976. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

The aim of this project has been to develop the field of group 4 indenyl metallocene complexes based upon highly methylated ligands. Previous studies have shown that these compounds can be extremely active ethylene polymerisation catalysts, and, as such, are of both significant academic and commercial interest <strong>Chapter One</strong> introduces metallocene chemistry, discussing developments within the field and the effects of permethylation on indenyl rings. A synopsis of the rise of the ansa-bridge is provided, in addition to highlights from recent zirconocene chemistry. A feature on olefin polymerisation is included, spanning heterogeneous catalysts, homogeneous metallocenes and post metallocenes, as well immobilised complexes and their supports. <strong>Chapter Two</strong> charts updates to syntheses of bridged and unbridged permethylindenyl ligands. The developments have allowed for their use as viable industrial procedures. <strong>Chapter Three</strong> is an account of the group 4 organometallic chemistry of the indenyl ligands from Chapter Two. Four bridged metallocenes, including rac-SBI*ZrCl₂ and meso-EBI*Zr(CH₂Ph)₂, are reported. In addition, six unbridged analogues comprising rac/meso-Ind^#<sub style='position: relative; left: -.8em;'>2</sub>MCl₂ (M = Zr, Hf) and rac/meso-Ind^#<sub style='position: relative; left: -.8em;'>2</sub>(CH₂Ph)₂ are described as well as a half-metallocene. The complexes are characterised by single crystal X-ray diffraction and variable temperature NMR spectroscopy. DFT calculations have been performed, with representations of their optimised geometries and frontier MOs given. <strong>Chapter Four</strong> describes a reliable, reproducible procedure for immobilising group 4 complexes on the surface of solid supports; in total 19 catalysts are prepared. In addition to SSMAO, two new inorganic supports (LDHMAO and Solid MAO) are utilised. The latter has never previously been described in the academic literature. These catalysts have been characterised by IR, UV/visible and solid-state NMR spectroscopy in addition to SEM imaging. Zr K-edge EXAFS experiments were conducted and exceptionally clear data are reported. <strong>Chapter Five</strong> investigates the aforementioned complexes as both solution- and slurry-phase ethylene polymerisation catalysts. Numerous parameters are tested including temperature and time dependence and all of the catalysts produce high molecular weight polymer in the range 150-300,000 daltons. The activity of rac SBI*ZrCl₂ in solution exceeds 22,500 kg_PE/mol_Zr/h/bar, and 7,500 kg_PE/molZr/h/bar immobilised on Solid MAO. meso-EBI*Zr(CH₂Ph)₂ displays double the activity of its dichloride analogue. 1-hexene co polymerisation is carried out as part of a high throughput screening study and activities in excess of 30,000 kg_PE/molZr/h/bar are reported. Scale-up polymerisation runs are also disclosed. The resultant polymer has been characterised by GPC, as well as X-ray diffraction, SEM, ¹³C NMR and IR spectroscopy. <strong>Chapter Six</strong> provides the experimental details and characterising data for the previous chapters. An Appendix consists of crystal structure data while the Electronic Appendix contains the CIFs, DFT output files and the raw polymerisation data.

This dissertation describes the synthesis, antimicrobial properties, and catalytic activity of a variety of eta5-ligand rhodium and iridium complexes. Cp*RM(beta-diketonato)Cl (Cp*R = R-substituted tetramethylcyclopentadienyl ligand) complexes were found to have selective activity against Mycobacterium smegmatis, with activity highly dependent upon the substituents on the Cp*R ligand as well as on the beta-diketonato ligand. These complexes were synthesized in good yield from the reaction of the chloro bridged dimers ([Cp*RMCl2]2) with the desired beta-diketonato ligand under basic conditions. All complexes were fully characterized by 1H and 13C NMR. Twenty single crystal X-ray structures were solved. The success of these syntheses led to investigation of another beta-diketonato ligand: 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac). Though many metal complexes of this ligand are known, reaction with [Cp*MCl2]2 did not yield the desired Cp*M(hfac)Cl complexes. Instead, a variety of products were obtained, three of which were characterized crystallographically. The most interesting structure featured a non-coordinating trifluoroacetate (TFA) anion and a [Cp*Ir]3Na1O4 cubane structure, which is an unprecedented and highly unusual arrangement for iridium. Attempts to synthesize this cluster rationally through reactions of [Cp*IrCl2]2 with TFA yielded instead a chloro bridged [Cp*IrCl(TFA)] dimer. Reaction of [Cp*MCl2]2 with 1,1,1-trifluoroacetylacetonate (tfac) yielded the expected Cp*M(tfac)Cl complex, indicating that the problem lies with using hfac as a ligand for Cp*M(III) complexes. Finally, the indenyl effect was investigated for the oxidative annulation of 2-phenylimidazole with 1-phenyl-1-propyne catalyzed by a series of methyl-substituted [(indenyl)RhCl2] dimers. [(Ind*)RhCl2]2 was found to have significantly greater activity than [Cp*RhCl2]2 (100% vs. 51%). Two plausible catalytic cycles were proposed, one of which invokes a ring slip transition state. Though it is unclear if the "indenyl effect" is responsible for this differing activity, it is certainly apparent that using an indenyl ligand has a notable effect in this catalytic reaction. Cyclometalation was also investigated stoichiometrically for 2-phenyl-1H-imidazole and 1-phenylpyrazole and found to proceed readily for [(Ind*)RhCl2]2. Additionally, the crystallographic structure of a Rh+ /Rh– ionic pair was solved. Ionic pairs such as this are rarely found in the literature. / Doctor of Philosophy / This dissertation deals with the uses of a series of unusual compounds containing the metals rhodium and iridium. Though these are rare and expensive metals, the uses and benefits described in this dissertation far outweigh the costs. Overall, the compounds described in this dissertation are colorfully characterized as “piano stool” compounds because of their overall shape and appearance. The metal, either rhodium or iridium, occupies a central point in the complex. On top of the metal is a “flat” organic group that gives the appearance of the seat of the piano stool. Below the metal, there are three other groups that look like the legs of the piano stool. By appropriate choice of the metals and the surrounding groups, special properties can be designed into these “piano stool” complexes. Chapter 2 describes the synthesis of a series of complexes where the “flat” group is a variant of a five-membered carbon ring compound known as cyclopentadienyl, the metal is rhodium or iridium, and two of the three legs come from a family of compounds known as acetylacetonates (acac). This series of piano stool compounds display antimicrobial activity against a class of pathogens known as mycobacteria, an example of which causes the disease tuberculosis. Changing the cyclopentadienyl group and the acac group allows for this antimicrobial activity to be tuned. In the following chapter, attempts to make the same type of compound described in the paragraph above with fluorine-substituted acacs gave some very unexpected results. The most surprising result was a very unusual cube-shaped structure containing 3 iridium atoms, 1 sodium atom, and 4 oxygen atoms, which is an unprecedented arrangement for iridium. Finally, there is a specific example of a flat group for the piano stool known as indenyl. Indenyl is intriguing because it can change shape from a flat group to a bent group. In doing this, it provides more space around the metal for other molecules to bind. The result of this work shows that piano stool compounds created with this indenyl group are more active and selective for carrying out a catalytic reaction to make new ring systems that could have potential use in the synthesis of new flavorings, fragrances, and even pharmaceuticals.

Four ethylene bis-indenyl ligands containing tethers of various lengths were successfully immobilized on the surface of functionalized silica gel. The strategy of immobilization was based on catalytic thiol-ene coupling of terminal alkene groups in the tethers with surface thiol groups. Obtained materials have high BET surface area and pore volume. The method developed can be used for immobilization of catalytically active bis-indenyl metallocene complexes, thus preventing their dimerization and deactivation.

Reactions of catalytic hydrogenations and polymerizations are widely used in industry for manufacture of fine chemicals, pharmaceuticals, and plastics. Homogeneous catalysts for the processes that have low stability and their separation is difficult. Therefore, the development of new highly active and stable catalysts for hydrogenations and polymerizations is a necessity. The objective of this research was the development of a strategy for immobilization of heterogeneous metallocene catalysts. First, a methodology of immobilization of bis-indenyl ligands on the surface of mesoporous silica gel was designed. Four bis-indenyl ligands containing functionalized tethers of various lengths with terminal alkene groups were synthesized. All bis-indenyl ligands were immobilized on the surface of mesoporous functionalized silica gel by two methods: hydrosilylation and thiol-ene coupling of the double bond. After comparing the results, the second strategy was chosen as more efficient. The materials can be used further as intermediates for synthesis of supported metallocene catalysts.

No description available.