| 18298114 |
Harkins SB, Mankad NP, Miller AJ, Szilagyi RK, Peters JC: Probing the electronic structures of [Cu2 (mu-XR2)] n+ diamond cores as a function of the bridging X atom (X = N or P) and charge (n = 0, 1, 2). J Am Chem Soc. 2008 Mar 19;130(11):3478-85. Epub 2008 Feb 26.
A series of dicopper diamond core complexes that can be isolated in three different oxidation states ([Cu2 (mu-XR2)] n+, where n = 0, 1, 2 and X = N or P) is described. Of particular interest is the relative degree of oxidation of the respective copper centers and the bridging XR2 units, upon successive oxidations. These dicopper complexes feature terminal phosphine and either bridging amido or phosphido donors, and as such their metal-ligand bonds are highly covalent. Cu K-edge, Cu L-edge, and P K-edge spectroscopies, in combination with solid-state X-ray structures and DFT calculations, provides a complementary electronic structure picture for the entire set of complexes that tracks the involvement of a majority of ligand-based redox chemistry. The electronic structure picture that emerges for these inorganic dicopper diamond cores shares similarities with the Cu2 (mu-SR) 2 CuA sites of cytochrome c oxidases and nitrous oxide reductases. |
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