The high-yielding synthesis and detailed characterization of two well-defined, linkage isomeric tripodal, tetradentate all-phosphorus ligands 1-3 is described. Coordination to Cu-I resulted in formation of complexes 4-6, for which the molecular structures indicate overall tridentate coordination to the copper atom in the solid state, with one dangling peripheral phosphine. The solution studies suggest fast exchange between the three phosphine side-arms. For these new Cu-I complexes, preliminary catalytic activity in the cyclopropanation of styrene with ethyldiazoacetate (EDA) is disclosed. The anticipated well-defined tetradentate coordination in a C-3-symmetric fashion was achieved with Rh-I and Ir-I leading to the overall five-coordinated complexes 7-12. Complex 11 has the norbomadiene (nbd) ligand coordinated in an unprecedented monodentate 2,3-eta(2) mode to Rh. Furthermore, unexpected but very interesting redox-chemistry and reactivity was displayed by the Rh(Cl)-complexes 7 and 8. Oxidation resulted in the formation of stable Rh-II metalloradicals [7]PF6 and [8]PF6 that were characterized by X-ray crystallography, magnetic susceptibility measurements, cyclic voltammetry, and electron paramagnetic resonance (ERR) spectroscopy. Subsequent redox-reactivity of these metalloradicals toward molecular hydrogen is described, resulting in the formation of Rh-III hydride compounds.