Generation and Reactivity of a Ni<sup>III</sup><sub>2</sub>(μ-1,2-peroxo) Complex

Zhao, Norman; Filatov, Alexander S.; Xie, Jiaze; Hill, Ethan A.; Rogachev, Andrey Yu.; Anderson, John S.

doi:10.1021/jacs.0c10958

Cited by 23 publications

(19 citation statements)

References 97 publications

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“…Recent work from Anderson and co-workers does suggest that the chloride ligand in starting complex 1 has moderate Lewis basicity as evidenced by coordination to an additional Na + cation. 16 We speculated that the origin of the observed reactivity to generate 4 may arise from the reaction of the bound chloride with electrophilic S 8 . To investigate whether advantageous chloride may yield higher amounts of 4, we added [Bu 4 N][Cl] in the presence of S 8 to compound 1.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…10 Sulfane sulfur insertion into Zn−S bonds can also be achieved with elemental sulfur as demonstrated by Ballesteros and Tsui and highlighted the role that redox inert metals may play in RSS regulation. 11 In this report we investigate the reactivity of phenyltris( 12 has been employed in the stabilization of highvalent metal-nitrido, 13 oxo, 14,15 and peroxo species, 16 as well as in studying the unusual seesaw geometries adapted by Ni II . 17 This coordination environment provides new opportunities to investigate how RSS interact with metals in such environments where simple ligand substitution reactions are generally expected, but due to geometric frustration, new reaction pathways are discovered.…”

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis of Terminal Bis(hydrosulfido) and Disulfido Complexes of Ni(II) from a Geometrically Frustrated Tetrahedral Ni(II) Chloride Complex

2021

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Recent studies have highlighted how reactive sulfur species (RSS) can be regulated and transported by metal–sulfur coordination compounds. We report herein the reactivity of PhB( t BuIm)3NiCl (1) with RSS, including the hydrosulfide anion ([Bu4N][SH]) and a reduced tetrasulfide ([K18-C-6]2[S4]). The strongly donating tris(carbene) ligand in 1 is geometrically constrained to a tetrahedral geometry, and the energetically preferable square planar geometry is not achievable with the [PhB( t BuIm)3]− ligand. Upon reaction of 1 with [Bu4N][SH] and [K18-C-6]2[S4], the square planar complexes PhB( t BuIm)2( t BuImH)Ni(SH)2 (2) and PhB( t BuIm)2( t BuImH)Ni(η2-S2) (3) are formed, respectively, via the protonation of one carbene ligand donor atom. Mechanistic investigation suggest that protonation occurs either from decomposition of 1 during the reaction progress, reactions with advantageous [Bu4N]+/[K18-C-6]+ countercations or from the generation of transient unidentified RSS that facilitate proton transfer reactions.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Synthesis of Terminal Bis(hydrosulfido) and Disulfido Complexes of Ni(II) from a Geometrically Frustrated Tetrahedral Ni(II) Chloride Complex

2021

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“…The two reported C P display paramagnetic NMR spectra and weak magnetic coupling for the Cu 2 O 2 core (PzTACN Me : ϕ

_{Cu_{2} normalO_{2}}

=62.5°, J =−77 cm −1 ; PzTACN Et : ϕ

_{Cu_{2} normalO_{2}}

=104.2°, J =+72 cm −1 ; H =‐2 J S 1 S 2 ) [7j, 14] due to interaction of the Cu II d

_{normalx^{2} - normaly^{2}}

orbitals with orthogonal π*(O 2 ) orbitals (Figure 4 c, right). Unfortunately, the thermal sensitivity of 2 has prevented our experimental determination of J through solid‐state magnetometry or fitting of variable temperature 1 H NMR spectra like other recent bimetallic peroxides, [7j, 14, 30] but a more detailed investigation of the electronic structure of 2 is warranted for future studies.…”

Section: Resultsmentioning

confidence: 99%

Calcium‐Ion Binding Mediates the Reversible Interconversion of Cis and Trans Peroxido Dicopper Cores

et al. 2021

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Coupled dinuclear copper oxygen cores (Cu2O2) featured in type III copper proteins (hemocyanin, tyrosinase, catechol oxidase) are vital for O2 transport and substrate oxidation in many organisms. μ‐1,2‐cis peroxido dicopper cores (CP) have been proposed as key structures in the early stages of O2 binding in these proteins; their reversible isomerization to other Cu2O2 cores are directly relevant to enzyme function. Despite the relevance of such species to type III copper proteins and the broader interest in the properties and reactivity of bimetallic CP cores in biological and synthetic systems, the properties and reactivity of CP Cu2O2 species remain largely unexplored. Herein, we report the reversible interconversion of μ‐1,2‐trans peroxido (TP) and CP dicopper cores. CaII mediates this process by reversible binding at the Cu2O2 core, highlighting the unique capability for metal‐ion binding events to stabilize novel reactive fragments and control O2 activation in biomimetic systems.

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“…Tetrahydrofuran (THF), THF- d 8 , and diethyl ether (Et 2 O) were stirred over NaK alloy and passed through a column of activated alumina prior to storing over 4 Å sieves under N 2 . PhB( Ad ImH) 3 OTf 2 and NaBAr F 4 were prepared according to previously reported procedures. , [HMTBD][BF 4 ] was synthesized according to a previously reported procedure . FcBF 4 and TBAPF 6 were recrystallized prior to use.…”

Section: Methodsmentioning

confidence: 99%

Enzyme-Like Hydroxylation of Aliphatic C–H Bonds From an Isolable Co-Oxo Complex

et al. 2021

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The selective hydroxylation of aliphatic C–H bonds remains a challenging but broadly useful transformation. Nature has evolved systems that excel at this reaction, exemplified by cytochrome P450 enzymes, which use an iron-oxo intermediate to activate aliphatic C–H bonds with k 1 > 1400 s–1 at 4 °C. Many synthetic catalysts have been inspired by these enzymes and are similarly proposed to use transition metal-oxo intermediates. However, most examples of well-characterized transition metal-oxo species are not capable of reacting with strong, aliphatic C–H bonds, resulting in a lack of understanding of what factors facilitate this reactivity. Here, we report the isolation and characterization of a new terminal CoIII-oxo complex, PhB(AdIm)3CoIIIO. Upon oxidation, a transient CoIV-oxo intermediate is generated that is capable of hydroxylating aliphatic C–H bonds with an extrapolated k 1 for C–H activation >130 s–1 at 4 °C, comparable to values observed in cytochrome P450 enzymes. Experimental thermodynamic values and DFT analysis demonstrate that, although the initial C–H activation step in this reaction is endergonic, the overall reaction is driven by an extremely exergonic radical rebound step, similar to what has been proposed in cytochrome P450 enzymes. The rapid C–H hydroxylation reactivity displayed in this well-defined system provides insight into how hydroxylation is accomplished by biological systems and similarly potent synthetic oxidants.

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Generation and Reactivity of a Ni^III₂(μ-1,2-peroxo) Complex

Cited by 23 publications

References 97 publications

Synthesis of Terminal Bis(hydrosulfido) and Disulfido Complexes of Ni(II) from a Geometrically Frustrated Tetrahedral Ni(II) Chloride Complex

Synthesis of Terminal Bis(hydrosulfido) and Disulfido Complexes of Ni(II) from a Geometrically Frustrated Tetrahedral Ni(II) Chloride Complex

Calcium‐Ion Binding Mediates the Reversible Interconversion of Cis and Trans Peroxido Dicopper Cores

Enzyme-Like Hydroxylation of Aliphatic C–H Bonds From an Isolable Co-Oxo Complex

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Generation and Reactivity of a NiIII2(μ-1,2-peroxo) Complex

Cited by 23 publications

References 97 publications

Synthesis of Terminal Bis(hydrosulfido) and Disulfido Complexes of Ni(II) from a Geometrically Frustrated Tetrahedral Ni(II) Chloride Complex

Synthesis of Terminal Bis(hydrosulfido) and Disulfido Complexes of Ni(II) from a Geometrically Frustrated Tetrahedral Ni(II) Chloride Complex

Calcium‐Ion Binding Mediates the Reversible Interconversion of Cis and Trans Peroxido Dicopper Cores

Enzyme-Like Hydroxylation of Aliphatic C–H Bonds From an Isolable Co-Oxo Complex

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Generation and Reactivity of a Ni^III₂(μ-1,2-peroxo) Complex