Transition Metal Hydrides Biomimetic Studies and Catalytic Applications

In this thesis, studies of the nature of different transition metal-hydride complexes are described. The first part deals with the enantioswitchable behaviour of rhodium complexes derived from amino acids, applied in asymmetric transfer hydrogenation of ketones. We found that the use of amino acid thio amide ligands resulted in the formation of the R -configured product, whereas the use of the corresponding hydroxamic acid- or hydrazide ligands selectively gave the S -alcohol. Structure/activity investigations revealed that the stereochemical outcome of the catalytic reaction depends on the ligand mode of coordination. In the second part, an Fe hydrogenase active site model complex with a labile amine ligand has been synthesized and studied. The aim of this study was to find a complex that efficiently catalyzes the reduction of protons to molecular hydrogen under mild conditions. We found that the amine ligand functions as a mimic of the loosely bound ligand which is part of the active site in the hydrogenase. Further, an Fe hydrogenase active site model complex has been coupled to a photosensitizer with the aim of achieving light induced hydrogen production. The redox properties of the produced complex are such that no electron transfer from the photosensitizer part to the Fe moiety occurs. In the last part of this thesis, the development of a protocol for the transfer hydrogenation of ketones to secondary alcohols without the involvement of transition metal catalysts is described. A variety of ketones were efficiently reduced in 2-propanol using catalytic amounts of alkali alkoxide under microwave irradiation. Härtill 5 uppsatser Diss. (sammanfattning) Stockholm : Stockholms universitet, 2007 Degree of Doctor of Technology teknisk doktorsexamen Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm Härtill 5 uppsatser Diss. (sammanfattning) Stockholm : Stockholms universitet, 2007 Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm In this thesis, studies of the nature of different transition metal-hydride complexes are described. The first part deals with the enantioswitchable behaviour of rhodium complexes derived from amino acids, applied in asymmetric transfer hydrogenation of ketones. We found that the use of amino acid thio amide ligands resulted in the formation of the R -configured product, whereas the use of the corresponding hydroxamic acid- or hydrazide ligands selectively gave the S -alcoho