2018
Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst
Rudshteyn B, Fisher K, Lant H, Yang K, Mercado B, Brudvig G, Crabtree R, Batista V. Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst. ACS Catalysis 2018, 8: 7952-7960. DOI: 10.1021/acscatal.8b02466.Peer-Reviewed Original ResearchKinetic isotope effectsWater nucleophilic attack mechanismWater oxidation catalystsWater nucleophilic attackD Kinetic Isotope EffectO bond formationUV-visible spectraDensity functional theoryElectrochemical stepWater oxidationElectrochemical analysisTurnover frequencyDerivative complexesBond formationRadical speciesRational designCis formFunctional theoryIsotope effectRate-limiting stepCatalystComplexesAttack mechanismMechanistic findingsDeprotonation
2015
Mechanism of Manganese-Catalyzed Oxygen Evolution from Experimental and Theoretical Analyses of 18O Kinetic Isotope Effects
Khan S, Yang K, Ertem M, Batista V, Brudvig G. Mechanism of Manganese-Catalyzed Oxygen Evolution from Experimental and Theoretical Analyses of 18O Kinetic Isotope Effects. ACS Catalysis 2015, 5: 7104-7113. DOI: 10.1021/acscatal.5b01976.Peer-Reviewed Original ResearchBiomimetic oxomanganese complexesO2 evolutionOxomanganese complexesElusive reaction intermediatesKinetic oxygen isotope effectO2-evolving complexPhotosystem IIFirst bindsTurnover conditionsPrevious kinetic studiesComplexesOxygen evolutionComplete mechanismEvolutionMechanismSpeciesBindsStrong evidenceIntermediatesTurnoverHighest barrier stepKinetic isotope effects