title: Structural and Spectroscopic Characterization of Reaction Intermediates Involved in a Dinuclear Co-Hbpp Water Oxidation Catalyst.
abstract: An end-on superoxido complex with the formula {[CoIII(OH2)(trpy)][CoIII(OO•)(trpy)](μ-bpp)}4+(34+) (bpp-= bis(2-pyridyl)-3,5-pyrazolate; trpy = 2,2';6':2″-terpyridine) has been characterized by resonance Raman, electron paramagnetic resonance, and X-ray absorption spectroscopies. These results together with online mass spectrometry experiments using17O and18O isotopically labeled compounds prove that this compound is a key intermediate of the water oxidation reaction catalyzed by the peroxido-bridged complex {[CoIII(trpy)]2(μ-bpp)(μ-OO)}3+(13+). DFT calculations agree with and complement the experimental data, offering a complete description of the transition states and intermediates involved in the catalytic cycle.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST) , Av. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Carolina
authors.initials: C
authors.lastname: Gimbert-Suriñach
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , 9700 South Cass Avenue, Lemont, Illinois 60439, United States.
authors.forename: Dooshaye
authors.initials: D
authors.lastname: Moonshiram
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST) , Av. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Laia
authors.initials: L
authors.lastname: Francàs
authors.affiliation: Department of Chemistry, Supercomputing Institute and Chemical Theory Center, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
authors.forename: Nora
authors.initials: N
authors.lastname: Planas
authors.affiliation: Department of Chemistry, Supercomputing Institute and Chemical Theory Center, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
authors.forename: Varinia
authors.initials: V
authors.lastname: Bernales
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST) , Av. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Fernando
authors.initials: F
authors.lastname: Bozoglian
authors.affiliation: International Research Center "Smart Materials", Southern Federal University , 344090 Rostov-on-Don, Russia.
authors.forename: Alexander
authors.initials: A
authors.lastname: Guda
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST) , Av. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Mognon
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST) , Av. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Isidoro
authors.initials: I
authors.lastname: López
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST) , Av. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Md Asmaul
authors.initials: MA
authors.lastname: Hoque
authors.affiliation: Department of Chemistry, Supercomputing Institute and Chemical Theory Center, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
authors.forename: Laura
authors.initials: L
authors.lastname: Gagliardi
authors.affiliation: Department of Chemistry, Supercomputing Institute and Chemical Theory Center, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Cramer
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST) , Av. Països Catalans 16, 43007 Tarragona, Spain.|Departament de Química, Universitat Autònoma de Barcelona , 08193 Cerdanyola del Vallès, Barcelona, Spain.
authors.forename: Antoni
authors.initials: A
authors.lastname: Llobet