MPI für bioanorganische Chemie / MPI für bioanorganische Chemie |
|Dioxygen Activation and Catalytic Reduction to Hydrogen Peroxide by a Thiolate-Bridged Dimanganese(II) Complex with a Pendant Thiol|
|Authors:||Gennari, Marcello; Brazzolotto, Deborah; Pecaut, Jacques; Cherrier, Mickael V.; Pollock, Christopher J.; DeBeer, Serena; Retegan, Marius; Pantazis, Dimitrios A.; Neese, Frank; Rouzieres, Mathieu; Clerac, Rodolphe; Duboc, Carole|
|Date of Publication (YYYY-MM-DD):||2015|
|Title of Journal:||Journal of the American Chemical Society|
|Issue / Number:||26|
|Review Status:||Internal review|
|Abstract / Description:||Herein, we describe an uncommon example of a manganese-thiolate complex, which is capable of activating dioxygen and catalyzing its two-electron reduction to generate H2O2. The structurally characterized dimercapto-bridged Mn-II dimer [Mn-2(II)(LS)(LSH)]ClO4 ((Mn2SH)-S-II) is formed by reaction of the LS ligand (2,2'-(2,2'-bipyridine-6,6'-diyl)bis-(1,1-diphenylethanethiolate)) with Mn-II. The unusual presence of a pendant thiol group bound to one Mn-II ion in (Mn2SH)-S-II is evidenced both in the solid state and in solution. The (Mn2SH)-S-II complex reacts with dioxygen in CH3CN, leading to the formation of a rare mono-mu-hydroxo dinuclear Mn-III complex, [(Mn-2(III)(LS)(2)(OH)]ClO4 ((Mn2OH)-O-III), which has also been structurally characterized. When (Mn2SH)-S-II reacts with O-2 in the presence of a proton source, 2,6-lutidinium tetrafluoroborate (up to 50 equiv), the formation of a new Mn species is observed, assigned to a bis-mu-thiolato dinudear Mn-III complex with two terminal thiolate groups (Mn-2(III)), with the concomitant production of H2O2 up to similar to 40% vs (Mn2SH)-S-II. The addition of a catalytic amount of (Mn2SH)-S-II to an air-saturated solution of Me(n)Fc (n = 8 or 10) and 2,6-lutidinium tetrafluoroborate results in the quantitative and efficient oxidation of Me(n)Fc by O-2 to afford the respective ferrocenium derivatives (Me(n)Fc(+), with n = 8 or 10). Hydrogen peroxide is mainly produced during the catalytic reduction of dioxygen with 80-84% selectivity, making the (Mn2SH)-S-II complex a rare Mn-based active catalyst for two-electron O-2 reduction.|
|Comment of the Author/Creator:||Date: 2015, JUL 8 2015|
|External Publication Status:||published|
|Version Comment:||Automatic journal name synchronization|
|Communicated by:||N. N.|
|Affiliations:||MPI für bioanorganische Chemie|
|External Affiliations:||[Gennari,M.; Brazzolotto,D.; Duboc,C.] Univ.Grenoble Alpes, CNRS UMR 5250, DCM, F-38000 Grenoble, France.
[Pecaut,J.] Univ.Grenoble Alpes, INAC SCIB, F-38000 Grenoble, France.
[Cherrier,M.V.] Univ.Grenoble Alpes, CNRS UMR 5075, CEA, Metalloprot Unit,Inst.Biol.Struct Jean Pierre Ebe, F-38027 Grenoble 1, France.
[Rouzieres,M.; Clerac,R.] CNRS, CRPP, UPR 8641, F-33600 Pessac, France.
[ 11 ] Univ Bordeaux, CRPP, UPR 8641, F-33600 Pessac, France.
|Identifiers:||ISI:000357964400052 [ID No:1] |
ISSN:0002-7863 [ID No:2]
DOI:10.1021/jacs.5b04917 [ID No:3]
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