title: Characterization of the O(2)-evolving reaction catalyzed by [(terpy)(H2O)Mn(III)(O)2Mn(IV)(OH2)(terpy)](NO3)3 (terpy = 2,2':6,2"-terpyridine).
abstract: The complex [(terpy)(H(2)O)Mn(III)(O)(2)Mn(IV)(OH(2))(terpy)](NO(3))(3) (terpy = 2,2':6,2' '-terpyridine) (1)catalyzes O(2) evolution from either KHSO(5) (potassium oxone) or NaOCl. The reactions follow Michaelis-Menten kinetics where V(max) = 2420 +/- 490 mol O(2) (mol 1)(-1) hr(-1) and K(M) = 53 +/- 5 mM for oxone ([1] = 7.5 microM), and V(max) = 6.5 +/- 0.3 mol O(2) (mol 1)(-1) hr(-1) and K(M) = 39 +/- 4 mM for hypochlorite ([1] = 70 microM), with first-order kinetics observed in 1 for both oxidants. A mechanism is proposed having a preequilibrium between 1 and HSO(5-) or OCl(-), supported by the isolation and structural characterization of [(terpy)(SO(4))Mn(IV)(O)(2)Mn(IV)(O(4)S)(terpy)] (2). Isotope-labeling studies using H(2)(18)O and KHS(16)O(5) show that O(2) evolution proceeds via an intermediate that can exchange with water, where Raman spectroscopy has been used to confirm that the active oxygen of HSO(5-) is nonexchanging (t(1/2) >> 1 h). The amount of label incorporated into O(2) is dependent on the relative concentrations of oxone and 1. (32)O(2):(34)O(2):(36)O(2) is 91.9 +/- 0.3:7.6 +/- 0.3:0.51 +/- 0.48, when [HSO(5-)] = 50 mM (0.5 mM 1), and 49 +/- 21:39 +/- 15:12 +/- 6 when [HSO(5-)] = 15 mM (0.75 mM 1). The rate-limiting step of O(2) evolution is proposed to be formation of a formally Mn(V)=O moiety which could then competitively react with either oxone or water/hydroxide to produce O(2). These results show that 1 serves as a functional model for photosynthetic water oxidation.
authors.affiliation: Contribution from the Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut, 06520-8107, USA.
authors.forename: J
authors.initials: J
authors.lastname: Limburg
authors.forename: J S
authors.initials: JS
authors.lastname: Vrettos
authors.forename: H
authors.initials: H
authors.lastname: Chen
authors.forename: J C
authors.initials: JC
authors.lastname: de Paula
authors.forename: R H
authors.initials: RH
authors.lastname: Crabtree
authors.forename: G W
authors.initials: GW
authors.lastname: Brudvig
mesh_terms: D002384:Catalysis; D006997:Hypochlorous Acid / Q000378:metabolism; D007700:Kinetics; D009942:Organometallic Compounds / Q000737:chemistry* / Q000378:metabolism; D016877:Oxidants / Q000378:metabolism; D010084:Oxidation-Reduction; D010100:Oxygen / Q000378:metabolism*; D010103:Oxygen Isotopes; D010126:Ozone / Q000378:metabolism; D045322:Photosynthetic Reaction Center Complex Proteins / Q000737:chemistry* / Q000378:metabolism; D013059:Spectrum Analysis, Raman
chemical_list: C118099:(H2O(terpy)Mn(O)2 Mn(terpy)OH2)(NO3)3; D009942:Organometallic Compounds; D016877:Oxidants; D010103:Oxygen Isotopes; D045322:Photosynthetic Reaction Center Complex Proteins; D010126:Ozone; D006997:Hypochlorous Acid; D010100:Oxygen