The well-known catalyst precursor 2,6-bis[1-((2,6-diisopropylphenyl)imino)ethyl]pyridine
(1) is functionalized by various alkenyl groups to yield the corresponding alkenyl-functionalized 2,6-bis[1-((2,6-diisopropylphenyl)imino)ethyl]pyridine ligand. Reaction of these
novel functionalized bis(imino)pyridyl ligands with iron(II) chloride results in the formation
of precatalysts 5−7, which possess different spacer moieties. The possibility of self-immobilization has been investigated with respect to the chain length of the alkenyl moiety.
Additionally, experiments to heterogenize these functionalized iron(II) complexes on modified
silica via hydrosilation are presented (8−10). The immobilization has been studied by IR,
and the resulting polymers have been characterized by GPC and static light scattering.
SummarySynthesis and characterization of the first organometallic Tc(VII) complex CH3TCO3 is described. It behaves differently to CHßReOs conccrning rcactions with alkenes and with aromatic amine bases. Furthermore we present the synthesis and structure of the first organometallic düster of Tc(I) Na[Tc3(CO)9(/i3-OCH3)(/i2-OCH3)3] with a cuban-like structure. The düster act as a crown ether with high stability towards sodium. In the crystal the difierent duster units are linked via an isocarbonyl bond. The düster proved to bc a useful educt for subsequent Substitution rcactions with tridentate ligands. Carbonylation of TBA[Tc04] under 1 atm CO fmally gave in quantitative yield, the very versatile educt mer-TcCl(CO)3[P(C6H5)3]2 which readily undergoes substitutions with several tridentate ligands.
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