Chapter 1.<br />1-Ethynyl-2-phenyltetramethyldisilanes HCºCSiMe2SiMe2C6H4-p-X [X = NMe2(1.1), Me (1.2), H (1.3), Br (1.4), CF3 (1.5)] are accessible from ClSiMe2SiMe2Cl, BrMgC6H4X and HCºCMgBr in a two step Grignard reaction. The crystal structure of 1.1 as determined by single crystal X-ray crystallography exhibits a nearly planar PhNMe2 moiety and an unusual gauche array of the phenyl and the acetylene group with respect to rotation around the Si-Si-bond. Full geometry optimization (B3LYP/6- 31+G**) of the gas phase structures of 1.1 and 1.3 affords minima for the gauche and the trans rotational isomers, both being very close in energy with a rotational barrier of only 3 – 5 kJ/mol. Experimental and calculated (time-dependent DFT B3LYP/TZVP) UV absorption data of 1.1 – 1.5 show pronounced electronic interactions of the HCºC- and the C6H4X p-systems with the central Si-Si bond.<br /><br />Chapter 2.<br />A family of [( 5-Cp*)Ru( 6-arene)]+ (Cp* = C5Me5) sandwich complexes of 1- and 1,4-substituted phenyl and naphthyl systems are described along with the regioselectivities of the reactions under various conditions. Finally, the (h 5-Cp*) Ru+ arenophile was found to act as a gate to the flow of electrons between para-substituted termini. When it is complexed onto the phenyl or A naphthyl ring, the gate is closed. On the contrary, when it is complexed onto the B naphthyl ring, the gate is open.<br /><br />Chapter 3.<br />Regioselective complexation reactions of the organoiron acetylide derivatives (h 2- dppe)(h 5-Cp*)Fe-C C-Ar (Ar = phenyl, 1-naphthyl; dppe = 1,2- bis(diphenylphosphino)ethane) with [(h 5-Cp*Ru(CH3CN)3][PF6] to afford heterobimetallic complexes formulated as [(h 2-dppe)(h 5-Cp*)Fe-C C-{(h 6-Ar)Ru(h 5- Cp*)}][PF6], were achieved. In the case of the FeII-RuII 1-naphthyl derivative, the (h 5-Cp*)Ru+ arenophile was complexed both onto the substituted ring and free rings of the acetylide 1-naphthyl linker. The first redox-driven h 6-h 6 inter-ring haptotropic migration of the (h 5-Cp*)Ru+ moeity was shown to occur. Crystal structures of all of the seven new iron acetylenes were resolved, including both haptotropomers of the naphthyl compound.<br /><br />Chapter 4.<br />The diorganoiron [{(h2-dpppe)(h5-Cp*)Fe-CC-}2(1,4-naphthyl)] (4.12) was synthesized in good yield in two steps via the vinylidene, and oxidation led to the mixed valence (MV) and iron(III)-iron(III) species in good to excellent yields. This exhaustive empirical study on the family of complexes 4.12[PF6]n (n = 0,1,2) includes a crystal structure for the case in which n = 2. This work clearly establishes good electronic and magnetic communication between the iron centers across the bis(ethynyl)naphthalene bridge. All empirical measurements of these naphthyl compounds reveal that their properties fall between those of known phenyl and anthracenyl derivatives. In some cases, the naphthyl derivative behaves as an average of the phenyl and anthracenyl complexes. For example, the comproportionation constant of the naphthyl species falls at the midpoint between those for the phenyl and anthracenyl compounds. The same is true for the UV absorption maxima in all three oxidation states (Fe[II]- Fe[II], MV, and Fe[III]- Fe[III]). The large electronic (2043 cm-1) and magnetic (-526 cm-1) coupling constants were determined via NIR spectroscopy and SQUID magnetometry, respectively. As for the heterotrinuclear species, the iron(II) acetylene, 4.14B[PF6] [{Cp*(dppe)Fe-C C}2-(h 6 – [1,4-napthyl])RuCp*](PF6), [Cp* = h 5 - C5Me5; Fe = FeII] was prepared in high yields with an adapted, regioselective synthesis via the trinuclear vinylidene. Complete characterization, including a crystal structure, of this sandwich complex reveals that the arenophile perturbs the organoiron ligand more in the bis(iron) than in the previously reported mono(iron) case.
| Identifer | oai:union.ndltd.org:CCSD/oai:tel.archives-ouvertes.fr:tel-00116762 |
| Date | 29 September 2006 |
| Creators | Shaw-Taberlet, Jennifer |
| Publisher | Université Rennes 1 |
| Source Sets | CCSD theses-EN-ligne, France |
| Language | English |
| Detected Language | English |
| Type | PhD thesis |
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