Organometallic chemistry of eta(6)-aromatic-cyclic-hydrocarbon manganese tricarbonyl complexes and electrochemical study of (arene)Cr(CO)(3) complexes having a pendent ferrocenyl switch

The important Mn{dollar}rmsp+(CO)sb3{dollar} organometallic moiety can be coordinated in an {dollar}etasp6{dollar}-fashion to aromatic organic ligands by three different methods. These synthetic routes involve a combination of acidic conditions and long reflux times at high temperatures. Thus organic ligands which are not thermally robust or contain acid sensitive functional groups are either difficult to coordinate or are coordinated in low yields and purity. The first part of this thesis focuses on the development of a manganese tricarbonyl transfer reagent which can mildly coordinate the Mn{dollar}rmsp+(CO)sb3{dollar} moiety to a variety of arene organic ligands. The reagent was based on the ring slippage effect, which is well known to occur in organometallic compounds such as (polyarene)Mn{dollar}rmsp+(CO)sb3{dollar}. Kinetic data from a variety of (polyarene)Mn{dollar}rmsp+(CO)sb3{dollar} complexes in a 1.0 M methylene chloride solution of acetonitrile were used to target the most promising compounds. Coordination of several representative arene compounds was then demonstrated under optimized conditions.; The second part of this thesis presents an application of manganese tricarbonyl mediated chemistry. A derivative of the aromatic steroid, 1-methylestrone, was synthesized in overall 43% yield starting with the readily available 3-methoxyestrone. The synthetic procedure involved the protection of the organic functionalities, coordination of the transition metal carbonyl (Mn{dollar}rmsp+(CO)sb3rbrack{dollar}, functionalisation of the arene ring, deprotection of the organic functional groups and final demetalation.; The final part of this thesis explores the electrochemical properties of a series of compounds based on a molecular system having an iron metal center covalently attached to a chromium metal center via an organic linker. Oxidation at the iron metal center (E{dollar}sb{lcub}1/2{rcub}{dollar} = 0.68 V) of the initial compound, {dollar}rm CPFe(Csb5Hsb4Csb6Hsb5)Cr(CO)sb3{dollar} (5-1a), in the presence of P(OEt){dollar}sb3{dollar} effectively induces reaction to occur at the chromium center (E{dollar}sb{lcub}1/2{rcub}{dollar} = 1.07 V), which has a higher oxidation potential than the iron center. Two different products could be detected electrochemically which were confirmed by electrochemical analysis of a genuine sample of each product. The identification allowed for an elaborate reaction pathway scheme to be compiled for (5-1a). Computer simulations of the cyclic-voltammograms were used to predict rate constants and provide theoretical evidence for the proposed pathway. A model was also proposed to try to explain how the induction effect could occur. Furthermore, this model was tested by the electrochemical characterization of several derivatives of (5-1a). By placing various substituents on the organic portions of (5-1a), the potentials could be adjusted so as to tune the reactivity of the system. It was also found that the reactivity could be effected by changing the organic linker. Experimental efforts were also made to try to determine if an intermolecular mechanism could account for the observations.