Abstract
The high-yielding synthesis and detailed characterization of two well-defined, linkage isomeric tripodal, tetradentate allphosphorus
ligands 1-3 is described. Coordination to CuI 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 CuI
complexes, preliminary catalytic activity in the cyclopropanation of styrene with ethyldiazoacetate (EDA) is disclosed. The
anticipated well-defined tetradentate coordination in a C3-symmetric fashion was achieved with RhI and IrI, leading to the
overall five-coordinated complexes 7-12. Complex 11 has the norbornadiene (nbd) ligand coordinated in an
unprecedented monodentate 2,3-η2 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 RhII metalloradicals
[7]PF6 and [8]PF6 that were characterized by X-ray crystallography, magnetic susceptibility measurements, cyclic
voltammetry, and electron paramagnetic resonance (EPR) spectroscopy. Subsequent redox-reactivity of these
metalloradicals toward molecular hydrogen is described, resulting in the formation of RhIII hydride compounds.
Original language | English |
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Pages (from-to) | 6495-6508 |
Number of pages | 14 |
Journal | Inorganic Chemistry |
Volume | 49 |
Issue number | 14 |
DOIs | |
Publication status | Published - 2010 |