Electronic Structure of the Water-Oxidation Catalyst [(bpy)2(OHx)RuORu(OHy)(bpy)2]z+: Weak Coupling between the Metal Centers Is Preferred over Strong Coupling
- 25 September 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (41) , 13222-13223
- https://doi.org/10.1021/ja0462427
Abstract
High-level DFT calculations indicate that the singlet ground state of the water-oxidizing blue Ru dimer [(bpy)2(OH2)RuIIIORuIII(OH2)(bpy)2]4+ is not due to a strong coupling of the excess electrons from each of the low-spin d5 RuIII centers across the Ru-O-Ru moiety, as has been assumed to date. Instead, broken symmetry orbital calculations suggest that a weak antiferromagnetically (AF) coupled singlet state is energetically more favorable by 10-35 kcal/mol. Experimentally observed redox potentials can only be reproduced if antiferromagnetic coupling is invoked.Keywords
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