2000
Kinetic analysis of the O2-forming reaction between [Mn(III)(dpa)2]− (dpa=dipicolinate) and potassium peroxomonosulfate
Limburg J, Crabtree* R, Brudvig* G. Kinetic analysis of the O2-forming reaction between [Mn(III)(dpa)2]− (dpa=dipicolinate) and potassium peroxomonosulfate. Inorganica Chimica Acta 2000, 297: 301-306. DOI: 10.1016/s0020-1693(99)00362-x.Peer-Reviewed Original ResearchO2-evolving complexPotassium peroxomonosulfateO2 evolutionComplexes of formulaO2-evolving reactionsFour-electron oxidationPhotosynthetic water oxidationPhotosystem IITerpy complexesWater oxidationManganese complexesKinetic analysisSide reactionsBond formationMolecular oxygenOxygen atomsReactionComplexesPeroxomonosulfateKey stepOxidationKobsManganeseTerpyridineTerpy
1999
A Functional Model for O-O Bond Formation by the O2-Evolving Complex in Photosystem II
Limburg J, Vrettos J, Liable-Sands L, Rheingold A, Crabtree R, Brudvig G. A Functional Model for O-O Bond Formation by the O2-Evolving Complex in Photosystem II. Science 1999, 283: 1524-1527. PMID: 10066173, DOI: 10.1126/science.283.5407.1524.Peer-Reviewed Original ResearchConceptsMolecular oxygenPhotosystem IIO bond formationPhotosynthetic water oxidationWater oxidationManganese dimerBond formationOxygen atomsActive siteIsotope labelingManganese ionsOxygenPhotosynthesisWaterSodium hypochloriteOxidationIonsFormationAtomsDimersComplexesO2Functional modelConversionHypochloriteA mechanistic and structural model for the formation and reactivity of a MnV[double bond, length half m-dash]O species in photosynthetic water oxidation
Limburg J, Szalai V, Brudvig G. A mechanistic and structural model for the formation and reactivity of a MnV[double bond, length half m-dash]O species in photosynthetic water oxidation. Dalton Transactions 1999, 0: 1353-1362. DOI: 10.1039/a807583b.Peer-Reviewed Original ResearchProtein complex photosystem IIPhotosynthetic water oxidationWater oxidationMn4 clusterModel complexesO bond-forming stepO bond-forming reactionsRedox-active tyrosine residueSubstrate water moleculesBond-forming reactionsO bond formationBond-forming stepHydrogen bond networkTetranuclear Mn clusterElectrophilic oxygen atomHydroxide ligandMnO speciesOrganic oxidationLength halfWater moleculesObserved reactivityBond formationNucleophilic attackOxygen atomsKey intermediate