Dioxygen activation by a novel manganese(II) thiolate complex with hydrotris(3,5-diisopropylpyrazol-1-yl)borate ligand

Komatsuzaki, Hidehito; Nagasu, Yuichi; Suzuki, Kantaro; Shibasaki, Takao; Satoh, Minoru; Ebina, Fujio; Hikichi, Shiro; Akita, Munetaka; Moro‐oka, Yoshihiko

doi:10.1039/a708210j

Cited by 15 publications

(9 citation statements)

References 13 publications

(10 reference statements)

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“…The spectrum of 1 shows base peak at m/z = 349 (100%) which is well assignable to the as an intermediate [32]. Another peak at m/z = 631 can be assigned to the mononuclear species [MnL 2 O 2 (3,5-DTBSQ)(CH 3 CN)].…”

Section: Electrospray Ionization Mass Spectral Studymentioning

confidence: 97%

Functional model for catecholase-like activity: A mechanistic approach with manganese(III) complexes of salen type Schiff base ligands

Seth

Drew

Ghosh

2012

Journal of Molecular Catalysis A: Chemical

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Section: Electrospray Ionization Mass Spectral Studymentioning

confidence: 97%

Functional model for catecholase-like activity: A mechanistic approach with manganese(III) complexes of salen type Schiff base ligands

Seth

Drew

Ghosh

2012

Journal of Molecular Catalysis A: Chemical

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“…For manganese, however, only one compound, based on pyrazolylborate skeleton and thus heavily loaded with nitrogen ligands, has been described [30]. The structure of 1, although unique among known Mn (d 5 ) thiolates closely follows that observed previously for cobalt(II) (d 7 ) [31] and zinc (d 10 ) [32] acetonitrile ligated tri-tert-butoxysilanethiolate complexes.…”

mentioning

confidence: 65%

The first manganese trialkoxysilanethiolates: Formation, properties and structure of solvent ligated complexes – [Mn{SSi(OBut)3}2(MeCN)] and [Mn{SSi(OBut)3}2(MeOH)4]

Kropidłowska¹,

Chojnacki²,

Becker³

2006

Inorganic Chemistry Communications

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“…However, dioxygen is usually kinetically inert and the direct transfer of an electron from the metal to oxygen occurs only when the reduction potential of the metal complex is more negative than that of O 2 (eq 1) Komatsuzaki and co-workers recently reported the oxygen activation in toluene by the Mn 2+ thiolate complex, yielding the Mn 3+ bis μ-O complex . They confirmed that the Mn carboxylate complex is ineffective under the same condition because carboxylate is not as an good electron donor as thiolate, which is capable of driving the reduction potential of the Mn complex negative enough for the oxygen activation.…”

Section: Resultsmentioning

confidence: 96%

Oxidation of the Sulfide Ligands to SO₄^2-in the Dinuclear Complex {RuCl[P(OMe)₃]₂}₂(μ-S₂)(μ-Cl)(μ-N₂H₄): Synthesis and Characterization of {RuCl[P(OMe)₃]₂}₂(μ-S₂)(μ-Cl)(μ-N₂H₄)⁺HSO₄^-, {RuCl₂[P(OMe)₃]₂}₂(μ-S)(μ-N₂H₄), and {RuCl[P(OMe)₃]₂
Matsumoto
¹
,
Koyama
²
,
Koide
³

1999
J. Am. Chem. Soc.
29
0
10
0
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The paramagnetic dinuclear Ru2+Ru3+ complex, {RuCl[P(OMe)3]2}2(μ-S2)(μ-Cl)(μ-N2H4) (1), reduces dioxygen by one-electron at room temperature in CH3CN to form 1 +O2 -, in which O2 - is coordinated to the μ-S2 ligand. The dioxygen reduction is preceded by protonation to yield HO2 + by the bridging hydrazine ligand. Complex 1 is electrochemically more negative than HO2 +, and a redox reaction generates 1 + and HO2 (→ O2 - + H+). Spectroscopic studies (NMR and UV−vis) show that 1 and 1 +O2 - are under equilibrium, and the succeeding disproportionation reaction of 1 +O2 - produces two intermediates, 1 + and the dithionite complex, 1 +(O2 -)2, as an intermediate. The dithionite intermediate undergoes Cl- dissociation and further oxidation to yield the dinuclear Ru complex {Ru2+Cl[P(OMe)3]2}2(μ-S2O5)(μ-N2H4) (3). The liberated Cl- attacks the dithionite complex, and induces SO4 2- dissociation to prepare the dinuclear complex {Ru3+Cl2[P(OMe)3]2}2(μ-S)(μ-N2H4) (5). On the other hand, intermediate 1 + forms an ion pair with HSO4 -, which stems from the liberated SO4 2-, to yield [{Ru3+Cl[P(OMe)3]2}2(μ-S2)(μ-Cl)(μ-N2H4)]+HSO4 - (4 = 1 +HSO4 -). A trace of {Ru3+Cl[P(OMe)3]2}2(μ-S2)(μ-Cl)2 (2) is also detected in the supernatant. The UV−vis spectroscopic study revealed that complexes 2−5 are the exclusive products and the oxidation reaction can be balanced as follows: 14 × 1 + 4.5 O2 = 2 + 5 × 3 + 4 × 4 + 4 × 5. The 18O2/16O2 mixed-labeled oxygen studies proved that the external oxygen was the source of oxygen for the formation of the S2O5 and HSO4 - groups in 3 and 4, respectively. The structures of 3, 4, and 5 are characterized by X-ray crystallographic structure determinations. The dinuclear framework of complex 4 remains identical with that of 1 except for the significantly shorter Ru−S distance. The hydrazine hydrogens of complex 3 show intramolecular hydrogen bonding, which is reflected on a significantly low field shift of the hydrazine 1H NMR resonance. Complex 3 possesses the μ-S2O5 2- ligand, in which the two μ-SO2-O,S ‘ bridges are linked at the sulfur atoms through the μ-oxo bonds. Comparison of the site symmetries around the Ru atoms of 1, 3, and 5 strongly supports the occurrence of coordination rearrangements.

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Dioxygen activation by a novel manganese(II) thiolate complex with hydrotris(3,5-diisopropylpyrazol-1-yl)borate ligand

Cited by 15 publications

References 13 publications

Functional model for catecholase-like activity: A mechanistic approach with manganese(III) complexes of salen type Schiff base ligands

Functional model for catecholase-like activity: A mechanistic approach with manganese(III) complexes of salen type Schiff base ligands

The first manganese trialkoxysilanethiolates: Formation, properties and structure of solvent ligated complexes – [Mn{SSi(OBut)3}2(MeCN)] and [Mn{SSi(OBut)3}2(MeOH)4]

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