2023
Electrocatalytic, Homogeneous Ammonia Oxidation in Water to Nitrate and Nitrite with a Copper Complex
Liu H, Lant H, Troiano J, Hu G, Mercado B, Crabtree R, Brudvig G. Electrocatalytic, Homogeneous Ammonia Oxidation in Water to Nitrate and Nitrite with a Copper Complex. ECS Meeting Abstracts 2023, MA2023-01: 2691-2691. DOI: 10.1149/ma2023-01552691mtgabs.Peer-Reviewed Original ResearchWater oxidationAmmonia oxidationO bond formationInitial mechanistic studiesMolecular catalystsCopper complexesMetal electrocatalystsFaradaic efficiencyAqueous mediaBond formationHigh selectivityOxidation processN2 productTitle reactionOxidationMechanistic studiesCatalysisComplexesRoom temperatureFriendly productionWaterElectrocatalystsElectrocatalyticNitrateCatalyst
2021
Observation of a potential-dependent switch of water-oxidation mechanism on Co-oxide-based catalysts
Lang C, Li J, Yang K, Wang Y, He D, Thorne J, Croslow S, Dong Q, Zhao Y, Prostko G, Brudvig G, Batista V, Waegele M, Wang D. Observation of a potential-dependent switch of water-oxidation mechanism on Co-oxide-based catalysts. Chem 2021, 7: 2101-2117. DOI: 10.1016/j.chempr.2021.03.015.Peer-Reviewed Original ResearchWater oxidation mechanismWater oxidation reactionWater nucleophilic attack mechanismCo-based catalystsO bond formationNucleophilic attack mechanismKey elementary stepsHeterogeneous catalystsSalt electrolyteElectrode potentialApplied potentialBond formationLow driving forceO couplingElementary stepsMechanistic switchCatalystHigh driving forceDriving forceReactionAttack mechanismWater activityElectrolyteHereinPotential
2019
Synthesis and Reactivity of Paramagnetic Nickel Polypyridyl Complexes Relevant to C(sp2)–C(sp3)Coupling Reactions
Beromi M, Brudvig G, Hazari N, Lant H, Mercado B. Synthesis and Reactivity of Paramagnetic Nickel Polypyridyl Complexes Relevant to C(sp2)–C(sp3)Coupling Reactions. Angewandte Chemie 2019, 131: 6155-6159. DOI: 10.1002/ange.201901866.Peer-Reviewed Original Research
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
Triplet Oxygen Evolution Catalyzed by a Biomimetic Oxomanganese Complex: Functional Role of the Carboxylate Buffer
Rivalta I, Yang K, Brudvig G, Batista V. Triplet Oxygen Evolution Catalyzed by a Biomimetic Oxomanganese Complex: Functional Role of the Carboxylate Buffer. ACS Catalysis 2015, 5: 2384-2390. DOI: 10.1021/acscatal.5b00048.Peer-Reviewed Original ResearchOxomanganese complexesTriplet oxygenOxygen evolutionWater splittingCatalytic oxygen evolutionO bond formationBiomimetic oxomanganese complexesNucleophilic water moleculeUnderlying reaction mechanismGreen plant chloroplastsPhotosynthetic oxygen evolutionWater ligandsCarboxylate ligandsInorganic coreMn complexesSuperoxo speciesNoninnocent roleCarboxylate groupsWater moleculesSubstrate waterBond formationSynthetic complexesCarboxylate buffersNucleophilic attackRedox potential
2013
3.15 Complex Systems: Photosynthesis
Pokhrel R, Brudvig G. 3.15 Complex Systems: Photosynthesis. 2013, 385-422. DOI: 10.1016/b978-0-08-097774-4.00313-2.Peer-Reviewed Original ResearchOxygen-evolving complexQuantum mechanics/molecular mechanicsPhotosystem IIOO bond formationDensity functional theory calculationsComplete catalytic cycleFunctional theory calculationsProton exit pathwayIron-sulfur centersMetal centerNatural photosynthesisModel complexesCatalytic cycleBond formationMolecular mechanicsFunctional mimicsElectronic characterizationTheory calculationsRole of chlorideOxygenic photosynthesisComplexesDetailed mechanismExit pathwayHydrogenasesPlastocyanin
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