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Radical Reactivity of the Fe(III)/(II) Tetramesitylporphyrin Couple: Hydrogen Atom Transfer, Oxyl Radical Dissociation, and Catalytic Disproportionation of a Hydroxylamine.

ABSTRACT: The chemistry of low-valent iron porphyrin complexes with oxyl radical reagents has been explored. (Meso-tetramesityl porphyrinato) iron(III) hydroxide, (TMP)FeIII(OH) reacts with the hydroxylamine TEMPO-H (1-hydroxy-2,2,6,6-tetramethylpiperdine) to yield the ferrous porphyrin, (TMP)FeII, together with H2O and TEMPO. This reaction has a second order rate constant k1 = 76 ± 5 M-1 1 s-1 and likely occurs by concerted e-/H+ transfer. Hydrazines PhNHNHPh and PhNHNH2 similarly yield (TMP)FeII. A subsequent reaction between TEMPO (2,2,6,6-tetramethylpiperdinyl radical) and (TMP)FeII is observed to reversibly form the TEMPO-ligated ferric porphyrin, (TMP)FeIII(TEMPO). A combination of 1H NMR and optical spectroscopies were used to determine the thermodynamic parameters for TEMPO binding: K4 (25°C) = 535 ± 20 M-1, ?H°4 = -7.0 ± 1.5 kcal mol-1, ?S°4= -11 ± 5 cal mol-1 K-1, ?G‡4(235K) = 21.3 ± 0.5 kcal mol-1, ?G‡-4(235K) = 16.9 ± 0.5 kcal mol-1. The Fe-O bond is remarkably weak. The stable phenoxyl radical 2,4,6- t Bu3C6H2O• (ArO•) forms a stronger bond to (TMP)FeII to irreversibly make a similar FeIII(OR) complex. Both (TMP)FeII and (TMP)FeIII(OH) are catalysts for the disproportionation of excess TEMPO-H to TEMPO and TEMP-H (2,2,6,6-tetramethylpiperdine). The lack of reactivity between (TMP)FeII and the alkylated TEMPO-H analogue, TEMPO-CH3, suggests that the disproportionation involves a hydrogen atom transfer step. These results highlight the importance and versatility of the heme FeIII/II couple that is often overshadowed by its higher-valent counterparts.

SUBMITTER: Porter TR

PROVIDER: S-EPMC3981745 | biostudies-literature | 2014 Jan

REPOSITORIES: biostudies-literature

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Radical Reactivity of the Fe(III)/(II) Tetramesitylporphyrin Couple: Hydrogen Atom Transfer, Oxyl Radical Dissociation, and Catalytic Disproportionation of a Hydroxylamine.

Porter Thomas R TR Mayer James M JM

Chemical science 20140101 1

The chemistry of low-valent iron porphyrin complexes with oxyl radical reagents has been explored. (Meso-tetramesityl porphyrinato) iron(III) hydroxide, (TMP)FeIII(OH) reacts with the hydroxylamine TEMPO-H (1-hydroxy-2,2,6,6-tetramethylpiperdine) to yield the ferrous porphyrin, (TMP)FeII, together with H2O and TEMPO. This reaction has a second order rate constant k1 = 76 ± 5 M-1 1 s-1 and likely occurs by concerted < ...[more]

PMID: 24729854

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Project description:Bimolecular rate constants have been measured for reactions that involve hydrogen atom transfer (HAT) from hydroxylamines to nitroxyl radicals, using the stable radicals TEMPO(*) (2,2,6,6-tetramethylpiperidine-1-oxyl radical), 4-oxo-TEMPO(*) (2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl radical), di-tert-butylnitroxyl ((t)Bu(2)NO(*)), and the hydroxylamines TEMPO-H, 4-oxo-TEMPO-H, 4-MeO-TEMPO-H (2,2,6,6-tetramethyl-N-hydroxy-4-methoxy-piperidine), and (t)Bu(2)NOH. The reactions have been monitored by UV-vis stopped-flow methods, using the different optical spectra of the nitroxyl radicals. The HAT reactions all have |DeltaG (o)| < or = 1.4 kcal mol(-1) and therefore are close to self-exchange reactions. The reaction of 4-oxo-TEMPO(*) + TEMPO-H --> 4-oxo-TEMPO-H + TEMPO(*) occurs with k(2H,MeCN) = 10 +/- 1 M(-1) s(-1) in MeCN at 298 K (K(2H,MeCN) = 4.5 +/- 1.8). Surprisingly, the rate constant for the analogous deuterium atom transfer reaction is much slower: k(2D,MeCN) = 0.44 +/- 0.05 M(-1) s(-1) with k(2H,MeCN)/k(2D,MeCN) = 23 +/- 3 at 298 K. The same large kinetic isotope effect (KIE) is found in CH(2)Cl(2), 23 +/- 4, suggesting that the large KIE is not caused by solvent dynamics or hydrogen bonding to solvent. The related reaction of 4-oxo-TEMPO(*) with 4-MeO-TEMPO-H(D) also has a large KIE, k(3H)/k(3D) = 21 +/- 3 in MeCN. For these three reactions, the E(aD) - E(aH) values, between 0.3 +/- 0.6 and 1.3 +/- 0.6 kcal mol(-1), and the log(A(H)/A(D)) values, between 0.5 +/- 0.7 and 1.1 +/- 0.6, indicate that hydrogen tunneling plays an important role. The related reaction of (t)Bu(2)NO(*) + TEMPO-H(D) in MeCN has a large KIE, 16 +/- 3 in MeCN, and very unusual isotopic activation parameters, E(aD) - E(aH) = -2.6 +/- 0.4 and log(A(H)/A(D)) = 3.1 +/- 0.6. Computational studies, using POLYRATE, also indicate substantial tunneling in the (CH(3))(2)NO(*) + (CH(3))(2)NOH model reaction for the experimental self-exchange processes. Additional calculations on TEMPO((*)/H), (t)Bu(2)NO((*)/H), and Ph(2)NO((*)/H) self-exchange reactions reveal why the phenyl groups make the last of these reactions several orders of magnitude faster than the first two. By inference, the calculations also suggest why tunneling appears to be more important in the self-exchange reactions of dialkylhydroxylamines than of arylhydroxylamines.

Dataset Information

Radical Reactivity of the Fe(III)/(II) Tetramesitylporphyrin Couple: Hydrogen Atom Transfer, Oxyl Radical Dissociation, and Catalytic Disproportionation of a Hydroxylamine.

Publications

Radical Reactivity of the Fe(III)/(II) Tetramesitylporphyrin Couple: Hydrogen Atom Transfer, Oxyl Radical Dissociation, and Catalytic Disproportionation of a Hydroxylamine.

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