Electronic Design Criteria for O−O Bond Formation via Metal−Oxo Complexes

@article{citeulike:2663343, abstract = {Abstract: Metaloxos are critical intermediates for the management of oxygen and its activation. The reactivity of the metaloxo is central to the formation of OO bonds, which is the essential step for oxygen generation. Two basic strategies for the formation of OO bonds at metaloxo active sites are presented. The acidbase (AB) strategy involves the attack of a nucleophilic oxygen species (e.g., hydroxide) on an electrophilic metaloxo. Here, active-site designs must incorporate the assembly of a hydroxide (or water) proximate to a high-valent metaloxo of even d electron count. For the radical coupling (RC) strategy, two high-valent metaloxos of an odd d electron count are needed to drive OO coupling. This Forum Article focuses on the different electronic structures of terminal metaloxos that support AB and RC strategies and the design of ligand scaffolds that engender these electronic structures.}, address = {Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, 6-335, Cambridge, Massachusetts 02139-4307, and Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138}, author = {Betley, Theodore A. and Wu, Qin and Van Voorhis, Troy and Nocera, Daniel G. }, citeulike-article-id = {2663343}, doi = {10.1021/ic701972n}, journal = {Inorg. Chem.}, keywords = {artificial\_photosynthesis, o-obond\_formation}, month = {March}, number = {6}, pages = {1849--1861}, posted-at = {2008-04-13 11:54:27}, priority = {2}, title = {Electronic Design Criteria for O\&\#x2212;O Bond Formation via Metal\&\#x2212;Oxo Complexes}, url = {http://dx.doi.org/10.1021/ic701972n}, volume = {47}, year = {2008} }

TY - JOUR ID - citeulike:2663343 L3 - citeulike-article-id:2663343 TI - Electronic Design Criteria for O−O Bond Formation via Metal−Oxo Complexes JF - Inorg. Chem. VL - 47 IS - 6 SP - 1849 EP - 1861 AD - Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, 6-335, Cambridge, Massachusetts 02139-4307, and Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138 N2 - Abstract: Metaloxos are critical intermediates for the management of oxygen and its activation. The reactivity of the metaloxo is central to the formation of OO bonds, which is the essential step for oxygen generation. Two basic strategies for the formation of OO bonds at metaloxo active sites are presented. The acidbase (AB) strategy involves the attack of a nucleophilic oxygen species (e.g., hydroxide) on an electrophilic metaloxo. Here, active-site designs must incorporate the assembly of a hydroxide (or water) proximate to a high-valent metaloxo of even d electron count. For the radical coupling (RC) strategy, two high-valent metaloxos of an odd d electron count are needed to drive OO coupling. This Forum Article focuses on the different electronic structures of terminal metaloxos that support AB and RC strategies and the design of ligand scaffolds that engender these electronic structures. KW - artificial_photosynthesis KW - o-obond_formation AU - Betley, Theodore AU - Wu, Qin AU - Van Voorhis, Troy AU - Nocera, Daniel PY - 2008/03/17/ UR - http://dx.doi.org/10.1021/ic701972n ER -