Hydrogen bonding interaction between imidazolyl N–H group and peroxide: Stabilization of Mn(III)-peroxo complex TpiPr2Mn(η2-O2)(imMeH) (imMeH=2-methylimidazole)

Singh, U. P.; Sharma, Asish K.; Hikichi, Shiro; Komatsuzaki, Hidehito; Moro‐oka, Yoshihiko; Akita, Munetaka

doi:10.1016/j.ica.2006.06.033

Cited by 41 publications

(63 citation statements)

References 16 publications

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“…The O-O bond length is 1.432(3) Å, which is typical of a peroxo ligand bound to a transition-metal ion and is in good agreement with other reported Mn III -O 2 complexes (Table 2). 22,27,14,24,30 Considering the peroxo as a monoligand, a τ parameter of 1.2 is obtained, indicating that this complex is at the trigonal bipyramidal limit, similar to other Tp-supported Mn III -O 2 adducts. 23 (The τ parameter of greater than 1, which would not be possible for authentic five-coordinate complexes, results from our specific definition of τ for Mn III -O 2 adducts.…”

Section: Resultsmentioning

confidence: 72%

“…In a recent review, 23 we noted that Mn III -O 2 adducts supported by the Tp i Pr2 ligand 22,27 represent a unique geometry compared to other mononuclear Mn III -O 2 adducts. Following a formalism proposed by Kitajima et al , 22 if the peroxo unit is viewed as a monoligand, the τ parameter, as defined in Scheme 1, may be used to classify Mn III -O 2 adducts along a spectrum of geometries from square pyramidal (τ = 0) to trigonal bipyramidal (τ = 1).…”

Section: Introductionmentioning

confidence: 99%

“…In contrast, a variety of synthetic peroxomanganese(III) species have been generated and characterized, offering insights into the structural, electronic, and reactivity properties of this class of compound. 14–27 Members of this class of compound include side-on peroxomanganese(III) adducts (Mn III -O 2 ) and end-on alkylperoxomanganese(III) adducts (Mn III -OOR). 28,29 …”

Section: Introductionmentioning

confidence: 99%

“…When this Mn III -O 2 complex was cooled from 253 to 193 K, the pz i Pr2 H ligand formed a hydrogen bond with one O atom of the peroxo unit, and this changed the absorption spectrum. 22,27 Specifically, the absorption maxima shifted from 561 to 583 nm (17 820 to 17 150 cm −1 ) causing the color of the complex to change from brown (at 253 K) to blue (at 193 K). In contrast, the frequency of the peroxo O-O vibration (ν O-O ), was not perturbed at all by this hydrogen bonding interaction.…”

Section: Introductionmentioning

confidence: 99%

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Geometric and electronic structure of a peroxomanganese(iii) complex supported by a scorpionate ligand

et al. 2014

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A monomeric MnII complex has been prepared with the facially-coordinating TpPh2 ligand, (TpPh2 = hydrotris(3,5-diphenylpyrazol-1-yl)borate). The X-ray crystal structure shows three coordinating solvent molecules resulting in a six-coordinate complex with Mn-ligand bond lengths that are consistent with a high-spin MnII ion. Treatment of this MnII complex with excess KO2 at room temperature resulted in the formation of a MnIII-O2 complex that is stable for several days at ambient conditions, allowing for the determination of the X-ray crystal structure of this intermediate. The electronic structure of this peroxomanganese(III) adduct was examined by using electronic absorption, electron paramagnetic resonance (EPR), low-temperature magnetic circular dichroism (MCD), and variable-temperature variable-field (VTVH) MCD spectroscopies. Density functional theory (DFT), time-dependent (TD)-DFT, and multireference ab initio CASSCF/NEVPT2 calculations were used to assign the electronic transitions and further investigate the electronic structure of the peroxomanganese(III) species. The lowest ligand-field transition in the electronic absorption spectrum of the MnIII-O2 complex exhibits a blue shift in energy compared to other previously characterized peroxomanganese(III) complexes that results from a large axial bond elongation, reducing the metal-ligand covalency and stabilizing the σ-antibonding Mn dz2 MO that is the donor MO for this transition.

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Section: Resultsmentioning

confidence: 72%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Geometric and electronic structure of a peroxomanganese(iii) complex supported by a scorpionate ligand

et al. 2014

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“…Similarly, the formation of a stable peroxomanganese(III) species derived from [(Tp iPr2 )Mn(μ-O)] 2 , which mimics certain aspects of the binding of molecular oxygen to the "distal" histidine residue in hemoglobin/myoglobin, was reported a few years ago [63].…”

Section: Tris(pyrazolyl)boratesmentioning

confidence: 80%

Synthetic Bioinorganic Chemistry: Scorpionates Turn 50

Rabinovich

2016

Structure and Bonding

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The coordination chemistry of scorpionates, anionic tripodal boroncentered ligands that readily bind to virtually all main group, transition, and f-block metals, has had a profound effect in the development of synthetic bioinorganic chemistry during the past 50 years. Highlighted in this article are some of the most meaningful results published in the area, primarily in the preparation of structural and functional model compounds for the active sites in metalloproteins and metalloenzymes, a theme that encompasses topics as diverse as nitrogen fixation and heavy metal poisoning. It has also been 50 years since the genesis of Structure and Bonding, so let this account also be a celebration of the many contributions that the staunch serial has had on the entire field of inorganic chemistry during the past half century.

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Structural and Spectroscopic Characterization of a Monomeric Side‐On Manganese(IV) Peroxo Complex

et al. 2012

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Erwischt: Über die Bindung und Aktivierung von Sauerstoff durch einen Mangankomplex wird berichtet. Eine PS3‐Koordinationssphäre, die um ein Mangan(I)‐Zentrum gebaut wurde, ermöglichte die Isolierung eines monomeren Mangan(IV)‐Peroxo‐Komplexes, der bei Raumtemperatur stabil ist (siehe Bild). Zum Mechanismus der Aktivierung molekularen Sauerstoffs wird eine MnII‐Zwischenstufe mit einer freien Koordinationsstelle zur Bindung des Substrats vorgeschlagen.

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Hydrogen bonding interaction between imidazolyl N–H group and peroxide: Stabilization of Mn(III)-peroxo complex TpiPr2Mn(η2-O2)(imMeH) (imMeH=2-methylimidazole)

Cited by 41 publications

References 16 publications

Geometric and electronic structure of a peroxomanganese(iii) complex supported by a scorpionate ligand

Geometric and electronic structure of a peroxomanganese(iii) complex supported by a scorpionate ligand

Synthetic Bioinorganic Chemistry: Scorpionates Turn 50

Structural and Spectroscopic Characterization of a Monomeric Side‐On Manganese(IV) Peroxo Complex

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