2023
Redox leveling of the Kok cycle of photosystem II established by water ligand binding to the oxygen evolving complex
Liu J, Yang K, Brudvig G, Batista V. Redox leveling of the Kok cycle of photosystem II established by water ligand binding to the oxygen evolving complex. Biophysical Journal 2023, 122: 199a-200a. DOI: 10.1016/j.bpj.2022.11.1210.Peer-Reviewed Original Research
2021
Organometallic complexes as preferred precursors to form molecular Ir(pyalk) coordination complexes for catalysis of oxygen evolution
Hu G, Crabtree R, Brudvig G. Organometallic complexes as preferred precursors to form molecular Ir(pyalk) coordination complexes for catalysis of oxygen evolution. Inorganica Chimica Acta 2021, 526: 120507. DOI: 10.1016/j.ica.2021.120507.Peer-Reviewed Original ResearchOrganometallic complexesCoordination complexesCatalyst precursorsOrganometallic ligandsOrganometallic precursorsOxygen evolution catalystsUseful catalyst precursorsBlue solutionPyalk ligandCoordination precursorsChelating ligandHomogeneous catalystsIrOx nanoparticlesActive speciesNanoparticle formationNanoparticle generationOxygen evolutionIsomeric mixtureOxidative activationCore unitLigandsCatalystComplexesActivation processPrecursors
2019
N,N,O Pincer Ligand with a Deprotonatable Site That Promotes Redox‐Leveling, High Mn Oxidation States, and a Mn2O2 Dimer Competent for Catalytic Oxygen Evolution
Lant H, Michaelos T, Sharninghausen L, Mercado B, Crabtree R, Brudvig G. N,N,O Pincer Ligand with a Deprotonatable Site That Promotes Redox‐Leveling, High Mn Oxidation States, and a Mn2O2 Dimer Competent for Catalytic Oxygen Evolution. European Journal Of Inorganic Chemistry 2019, 2019: 2115-2123. DOI: 10.1002/ejic.201801343.Peer-Reviewed Original ResearchAlkoxide moietyOxidation stateOxygen evolutionHigher Mn oxidation statesCatalytic oxygen evolutionO-pincer ligandMn oxidation statePincer ligandRedox levelingElectrochemical dataLow overpotentialProtonation stateProton lossEPR experimentsMn IIIO intermediateRelated seriesMn–VMn IIMoietyLigandsOverpotentialDicationCatalystCatalysisModification of a pyridine-alkoxide ligand during the synthesis of coordination compounds
Shopov D, Sharninghausen L, Sinha S, Mercado B, Brudvig G, Crabtree R. Modification of a pyridine-alkoxide ligand during the synthesis of coordination compounds. Inorganica Chimica Acta 2019, 484: 75-78. DOI: 10.1016/j.ica.2018.09.020.Peer-Reviewed Original ResearchPyridine-alkoxide ligandsWater oxidation catalysisHigher oxidation statesCoordination compoundsPincer ligandGeminal methyl groupsCatalytic conditionsOxidation stateOxidation catalystReaction conditionsMinor byproductsAliphatic alkenesMinor productsOxidative conditionsMethyl groupN-oxideLigandsBlue solutionCH groupPincerStructural analoguesSynthesisComplexesCatalystCentral unit
2018
Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO2 Conversion to CO
Jiang J, Matula A, Swierk J, Romano N, Wu Y, Batista V, Crabtree R, Lindsey J, Wang H, Brudvig G. Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO2 Conversion to CO. ACS Catalysis 2018, 8: 10131-10136. DOI: 10.1021/acscatal.8b02991.Peer-Reviewed Original ResearchCO Faradaic efficiencyAg/AgClBulk electrolysisMA/cm2Organic ligandsFaradaic efficiencyReductive catalysisRobust electrocatalystsPorphyrin counterpartsDFT calculationsSevere stability issuesCO2 conversionCO2 reductionReductive conditionsUnusual stabilityCatalytic stepLigand degradationTotal current densityMolecular originCurrent densityElectrocatalystsCO2 fixationLigandsObserved stabilityBioinspired studyCatalysing water oxidation using nature’s metal
Brudvig G. Catalysing water oxidation using nature’s metal. Nature Catalysis 2018, 1: 10-11. DOI: 10.1038/s41929-017-0013-1.Peer-Reviewed Original Research
2017
Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O‐Donor Organic Ligand
Sharninghausen L, Sinha S, Shopov D, Mercado B, Balcells D, Brudvig G, Crabtree R. Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O‐Donor Organic Ligand. Angewandte Chemie 2017, 129: 13227-13231. DOI: 10.1002/ange.201707593.Peer-Reviewed Original ResearchCoordination complexesO-donor organic ligandsMononuclear coordination complexesO-donor environmentMetal-centered oxidationX-ray crystallographyOrganic ligandsDonor strengthAlkoxide groupsDFT calculationsD orbitalsUnprecedented stabilityComplexesLigandsOxidationIR-VIsomersXPSCrystallographyV complexSynthesisCharacterizationStabilityCalculationsDegradationAntimony Complexes for Electrocatalysis: Activity of a Main‐Group Element in Proton Reduction
Jiang J, Materna K, Hedström S, Yang K, Crabtree R, Batista V, Brudvig G. Antimony Complexes for Electrocatalysis: Activity of a Main‐Group Element in Proton Reduction. Angewandte Chemie 2017, 129: 9239-9243. DOI: 10.1002/ange.201704700.Peer-Reviewed Original ResearchMain group catalysisRedox-active ligandsMain group complexesQuantum chemistry calculationsMain group elementsViable electrocatalystsPorphyrin ligandChemistry calculationsHydroxy ligandsElectrocatalysis applicationsProton reductionCatalytic propertiesAntimony complexesRedox activityAxial ligandsCatalytic cycleSb centerLigandsCatalysisComplexesElectrocatalysisElectrocatalystsPorphyrinsReactionAcidElectrocatalytic Water Oxidation by a Copper(II) Complex of an Oxidation-Resistant Ligand
Fisher K, Materna K, Mercado B, Crabtree R, Brudvig G. Electrocatalytic Water Oxidation by a Copper(II) Complex of an Oxidation-Resistant Ligand. ACS Catalysis 2017, 7: 3384-3387. DOI: 10.1021/acscatal.7b00494.Peer-Reviewed Original ResearchWater oxidationElectrocatalytic water oxidationPotential electrolysis experimentsWater oxidation electrocatalystsStrong donor characterCatalyst degradationTurnover frequencyElectrolysis experimentsDonor characterCatalytic turnoverBasic conditionsOxidationHarsh conditionsOxidation resistanceElectrocatalystsCatalystLigandsCopperComplexesO2NHEFormationDegradationSynthesis of pyridine-alkoxide ligands for formation of polynuclear complexes
Shopov D, Sharninghausen L, Sinha S, Borowski J, Mercado B, Brudvig G, Crabtree R. Synthesis of pyridine-alkoxide ligands for formation of polynuclear complexes. New Journal Of Chemistry 2017, 41: 6709-6719. DOI: 10.1039/c7nj01845b.Peer-Reviewed Original ResearchO-donor ligandsPolynuclear complexesFirst-row transition metalsPyridine-alkoxide ligandsInexpensive starting materialsOne-step synthesisX-ray crystallographyPolynuclear clustersTransition metalsStarting materialScalable procedureGeneral formulaLigandsEffective bindingLarge-scale productionLigand 2Chelation powerComplexesSynthesisDenticityCluster formationDeprotonationFormationCrystallographyChromatography
2015
Comparison of dppf‐Supported Nickel Precatalysts for the Suzuki–Miyaura Reaction: The Observation and Activity of Nickel(I)
Guard L, Beromi M, Brudvig G, Hazari N, Vinyard D. Comparison of dppf‐Supported Nickel Precatalysts for the Suzuki–Miyaura Reaction: The Observation and Activity of Nickel(I). Angewandte Chemie 2015, 127: 13550-13554. DOI: 10.1002/ange.201505699.Peer-Reviewed Original ResearchSuzuki–Miyaura reactionNi II complexesSimilar catalytic activityDppf ligandNickel precatalystsNi precatalystsOxidation stateCatalytic activityPrecatalystHeterocyclic substratesNi 0Potential chemicalI speciesReactionII complexesRoom temperaturePd systemLigandsComplexesChemicalsNiSignificant amountSubstrate
2013
Synthesis and Properties of NHC-Supported Palladium(I) Dimers with Bridging Allyl, Cyclopentadienyl, and Indenyl Ligands
Dai W, Chalkley M, Brudvig G, Hazari N, Melvin P, Pokhrel R, Takase M. Synthesis and Properties of NHC-Supported Palladium(I) Dimers with Bridging Allyl, Cyclopentadienyl, and Indenyl Ligands. Organometallics 2013, 32: 5114-5127. DOI: 10.1021/om400687m.Peer-Reviewed Original Research
2012
A tridentate Ni pincer for aqueous electrocatalytic hydrogen production
Luca O, Konezny S, Blakemore J, Colosi D, Saha S, Brudvig G, Batista V, Crabtree R. A tridentate Ni pincer for aqueous electrocatalytic hydrogen production. New Journal Of Chemistry 2012, 36: 1149-1152. DOI: 10.1039/c2nj20912h.Peer-Reviewed Original Research
2011
An Iridium(IV) Species, [Cp*Ir(NHC)Cl]+, Related to a Water-Oxidation Catalyst
Brewster T, Blakemore J, Schley N, Incarvito C, Hazari N, Brudvig G, Crabtree R. An Iridium(IV) Species, [Cp*Ir(NHC)Cl]+, Related to a Water-Oxidation Catalyst. Organometallics 2011, 30: 965-973. DOI: 10.1021/om101016s.Peer-Reviewed Original ResearchWater oxidation catalystsOne-electron stepsX-ray crystallographyWingtip groupsElectrochemical characterizationLigand environmentElectrochemical behaviorOxidation stateEPR spectroscopyNew compoundsCatalystRhombic symmetryCompoundsΚ2 CC donorsPrecatalystNHCChelatesCrystallographySpectroscopyLigandsCatalyticPrecursorsCharacterizationWater
2008
Functional Manganese Model Chemistry Relevant to the Oxygen-Evolving Complex of Photosystem II: Oxidation of a Mn(III,IV) Complex Coupled to Deprotonation of a Terminal Water Ligand
Cady C, Crabtree R, Brudvig G. Functional Manganese Model Chemistry Relevant to the Oxygen-Evolving Complex of Photosystem II: Oxidation of a Mn(III,IV) Complex Coupled to Deprotonation of a Terminal Water Ligand. 2008, 377-381. DOI: 10.1007/978-1-4020-6709-9_85.Peer-Reviewed Original ResearchTerminal water ligandsWater ligandsDinuclear manganese complexPH-dependent oxidationOxygen-Evolving ComplexRedox stepsManganese complexesRedox levelingElectron transferModel chemistryTerminal waterLigandsOxidationDeprotonationComplex occursComplexesPhotosystem IIChemistryProtonsMVPHWaterNarrow rangeTransfer
2005
High‐Spin Chloro Mononuclear MnIII Complexes: A Multifrequency High‐Field EPR Study
Mantel C, Chen H, Crabtree R, Brudvig G, Pécaut J, Collomb M, Duboc C. High‐Spin Chloro Mononuclear MnIII Complexes: A Multifrequency High‐Field EPR Study. ChemPhysChem 2005, 6: 541-546. PMID: 15799481, DOI: 10.1002/cphc.200400484.Peer-Reviewed Original ResearchConceptsElectronic propertiesLigand field strengthHigh-Field EPR StudyPorphyrinic systemsTridentate ligandMnIII complexesDistorted octahedronLigands decreasesSolid stateJahn-Teller distortionPrevious complexesStructural characterizationCrystallographic dataEPR studiesMultifrequency EPRManganese ionsComplexesOctahedraTetragonal distortionE termDifferent temperaturesAnionsEPRLigandsProperties
2002
Two New Terpyridine Dimanganese Complexes: A Manganese(III,III) Complex with a Single Unsupported Oxo Bridge and a Manganese(III,IV) Complex with a Dioxo Bridge. Synthesis, Structure, and Redox Properties
Baffert C, Collomb M, Deronzier A, Pécaut J, Limburg J, Crabtree R, Brudvig G. Two New Terpyridine Dimanganese Complexes: A Manganese(III,III) Complex with a Single Unsupported Oxo Bridge and a Manganese(III,IV) Complex with a Dioxo Bridge. Synthesis, Structure, and Redox Properties. Inorganic Chemistry 2002, 41: 1404-1411. PMID: 11896708, DOI: 10.1021/ic0107375.Peer-Reviewed Original ResearchConceptsOxo bridgeElectrochemical behaviorX-ray structureMononuclear complexesComplexes 4Oxo complexesRedox propertiesAqua complexesDimanganese complexesOrganic mediaTrans complexesCis geometrySolid stateDioxo bridgeTrans geometryCis complexesDisproportionation processTrans configurationCrystallographic formsComplexesMn atomsCisMonooxoLigandsSynthesis
1998
Synthesis and characterization of an internal emission standard and applications to fluorescence studies of photosystem II
Schweitzer R, Brudvig G. Synthesis and characterization of an internal emission standard and applications to fluorescence studies of photosystem II. Biopolymers 1998, 2: 167-171. DOI: 10.1002/(sici)1520-6343(1996)2:3<167::aid-bspy3>3.0.co;2-5.Peer-Reviewed Original ResearchChelate complexesFluorescence intensityFluorescence measurementsDiethylenetriaminepentaacetic acid derivativeTerbium luminescenceAqueous phaseTerbium emissionAcid derivativesPyrimidine ringComplexesPhotosystem II functionLow temperaturePhotosynthetic organismsLow absorptionCryogenic temperaturesLanthanidesDifferent samplesLigandsSynthesisLuminescenceTerbiumTemperatureDerivativesPurificationEmission standardsIdentification of Histidine 118 in the D1 Polypeptide of Photosystem II as the Axial Ligand to Chlorophyll Z †
Stewart D, Cua A, Chisholm D, Diner B, Bocian D, Brudvig G. Identification of Histidine 118 in the D1 Polypeptide of Photosystem II as the Axial Ligand to Chlorophyll Z †. Biochemistry 1998, 37: 10040-10046. PMID: 9665709, DOI: 10.1021/bi980668e.Peer-Reviewed Original ResearchConceptsElectron paramagnetic resonanceAxial ligandsChlorophyll ZPhotosystem IIRR spectraLow-temperature electron paramagnetic resonanceWild-type Photosystem IIRedox-active tyrosinesReaction centersEfficiency of photooxidationResonance Raman spectroscopyPSII complexesIR absorbance spectraD2 polypeptidesBacterial reaction centersParamagnetic resonanceRR signatureRaman spectroscopyAccessory ChlInfrared absorbanceQuantum yieldAbsorbance bandLigandsIR excitationLow-temperature illumination
1991
The chemistry of high-valent oxomanganese clusters in aqueous solution: A (IV,IV) dimer containing bridging and terminal phosphate ligands
Sarneski J, Didiuk M, Thorp H, Crabtree R, Brudvig G, Faller J, Schulte G. The chemistry of high-valent oxomanganese clusters in aqueous solution: A (IV,IV) dimer containing bridging and terminal phosphate ligands. Journal Of Inorganic Biochemistry 1991, 43: 372. DOI: 10.1016/0162-0134(91)84358-g.Peer-Reviewed Original Research