NO sorption, in-crystal nitrite and nitrate production with arylamine oxidation in gas–solid single crystal to single crystal reactions

Møller, Mads Sondrup; Haag, Alexander; McKee, Vickie; McKenzie, Christine J.

doi:10.1039/c9cc05315h

Cited by 4 publications

(13 citation statements)

References 21 publications

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“…The NO binds reversibly, and the materials do not allow O 2 to react with the bound NO. This supports the hypothesis that the in-crystal reactivity seen for the crystalline dicobalt(II) complexes described in the introduction, where sorbed NO and O 2 were transformed to a nitrite ligand and a nitrate counter anion [7], is dependent on two cobalt(II) ions in close proximity. Accessibility and the specific coordination sphere and geometry, however, also clearly play important roles.…”

Section: Supplementary Materialssupporting

confidence: 86%

“…Chemisorptive processes can result in the transformation of the sorbed NO into less toxic compounds and precedence for this was demonstrated recently using the crystalline solid-state of a dicobalt(II) complex, which co-chemisorbs NO and O 2 . Accompanied by metal oxidation, their conversion to a coordinated nitrite and nitrate counter anion ensues through a series of unidentified in-crystal reactions [7].…”

Section: Introductionmentioning

confidence: 99%

“…We were interested in investigating the chemisorptive reactivity of NO by an isolated mononuclear Co(II) site inside the crystalline lattice of a molecular solid in efforts to understand the mechanism of the host-guest, solid-gas chemistry of the aforementioned molecular dicobalt(II) complexes [7]. In particular, we wanted to investigate whether the in-crystal conversion of NO and O 2 to NO 2 − and NO 3 is dependent on the presence of two closely-located cobalt ions working cooperatively to activate these guest substrates.…”

Section: Introductionmentioning

confidence: 99%

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Solid Phase Nitrosylation of Enantiomeric Cobalt(II) Complexes

et al. 2021

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Accompanied by a change in color from red to black, the enantiomorphic phases of the cobalt complexes of a chiral salen ligand (L2−, Co(L)·CS2, and Co(L) (L = LS,S or LR,R)) chemisorb NO (g) at atmospheric pressure and rt over hours for the CS2 solvated phase, and within seconds for the desolvated phase. NO is installed as an axial nitrosyl ligand. Aligned but unconnected voids in the CS2 desorbed Co(LR,R)·CS2 structure indicate conduits for the directional desorption of CS2 and reversible sorption of NO, which occur without loss of crystallinity. Vibrational circular dichroism (VCD) spectra have been recorded for both hands of LH2, Zn(L), Co(L)·CS2, Co(L), Co(NO)(L), and Co(NO)(L)·CS2, revealing significant differences between the solution-state and solid-state spectra. Chiral induction enables the detection of the νNO band in both condensed states, and surprisingly also the achiral lattice solvent (CS2 (νCS at 1514 cm−1)) in the solid-state VCD. Solution-state spectra of the paramagnetic Co(II) complex shows a nearly 10-fold enhancement and more extensive inversion of polarity of the vibrations of dominant VCD bands compared to the spectra of the diamagnetic compounds. This enhancement is less pronounced when there are fewer polarity inversions in the solid state VCD spectra.

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Section: Supplementary Materialssupporting

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Solid Phase Nitrosylation of Enantiomeric Cobalt(II) Complexes

et al. 2021

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“…The addition of H 2 to 6 to form 7 also results in a change in the oxidation state of the metal, accompanied by a move from pseudo square planar to octahedral. SC-SC transformations that involve an overall change in oxidation state have been reported previously, 10 for example, Mn(II)/Mn(IV); 60 Co(II)/Co(III); 61 Rh(I)/Rh(III); 13 , 62 , 63 Ir(I)/Ir(III); 21 Ir(III)/Ir(V); 64 and Au(I)/Au(III). 65 …”

Section: Resultsmentioning

confidence: 59%

Single-Crystal to Single-Crystal Addition of H₂ to [Ir(ⁱPr-PONOP)(propene)][BAr^F₄] and Comparison Between Solid-State and Solution Reactivity

et al. 2022

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The reactivity of the Ir(I) PONOP pincer complex [Ir( i Pr-PONOP)(η 2 -propene)][BAr F 4 ], 6, [ i Pr-PONOP = 2,6-( i Pr 2 PO) 2 C 6 H 3 N, Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ] was studied in solution and the solid state, both experimentally, using molecular density functional theory (DFT) and periodic-DFT computational methods, as well as in situ single-crystal to single-crystal (SC-SC) techniques. Complex 6 is synthesized in solution from sequential addition of H 2 and propene, and then the application of vacuum, to [Ir( i Pr-PONOP)(η 2 -COD)][BAr F 4 ], 1, a reaction manifold that proceeds via the Ir(III, 2, and the Ir(III) dihydride propene complex [Ir( i Pr-PONOP)(η 2 -propene)H 2 ][BAr F 4 ], 7, respectively. In solution (CD 2 Cl 2 ) 6 undergoes rapid reaction with H 2 to form dihydride 7 and then a slow (3 d) onward reaction to give dihydrogen/dihydride 2 and propane. DFT calculations on the molecular cation in solution support this slow, but productive, reaction, with a calculated barrier to rate-limiting propene migratory insertion of 24.8 kcal/mol. In the solid state single-crystals of 6 also form complex 7 on addition of H 2 in an SC-SC reaction, but unlike in solution the onward reaction (i.e., insertion) does not occur, as confirmed by labeling studies using D 2 . The solid-state structure of 7 reveals that, on addition of H 2 to 6, the PONOP ligand moves by 90°within a cavity of [BAr F 4 ] − anions rather than the alkene moving. Periodic DFT calculations support the higher barrier to insertion in the solid state (ΔG ‡ = 26.0 kcal/mol), demonstrating that the single-crystal environment gates onward reactivity compared to solution. H 2 addition to 6 to form 7 is reversible in both solution and the solid state, but in the latter crystallinity is lost. A rare example of a sigma amine-borane pincer complex, [Ir( i Pr-PONOP)H 2 (η 1 -H 3 B•NMe 3 )][BAr F 4 ], 5, is also reported as part of these studies.

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“…It may also be challenging due to the low water solubility of nitric oxide, resulting in high water consumption and unwanted degradation of oxidizing agents . At the same time, selective sorption of nitric oxide is a perspective route devoid of such drawbacks, − and application of modified mesoporous silica is a particularly promising way in this direction. To realize this approach, organic molecules able to interact with nitrogen monoxide in a reversible manner have to be found.…”

Section: Introductionmentioning

confidence: 99%

Blatter Radical-Decorated Silica as a Prospective Adsorbent for Selective NO Capture from Air

Poryvaev

Gjuzi

Yazikova

et al. 2023

ACS Appl. Mater. Interfaces

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Nitrogen oxides are adverse poisonous gases present in the atmosphere and having detrimental effects on the human health and environment. In this work, we propose a new type of mesoporous materials capable of capturing nitrogen monoxide (NO) from air. The designed material combines the robust Santa Barbara Amorphous-15 silica scaffold and ultrastable Blatter-type radicals acting as NO traps. Using in situ electron paramagnetic resonance spectroscopy, we demonstrate that NO capture from air is selective and reversible at practical conditions, thus making Blatter radical-decorated silica highly promising for environmental applications.

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NO sorption, in-crystal nitrite and nitrate production with arylamine oxidation in gas–solid single crystal to single crystal reactions

Abstract: Chemisorptive capture and in-crystal conversions of NO at dicobalt site SC–SC reactions.

Cited by 4 publications

References 21 publications

Solid Phase Nitrosylation of Enantiomeric Cobalt(II) Complexes

Solid Phase Nitrosylation of Enantiomeric Cobalt(II) Complexes

Single-Crystal to Single-Crystal Addition of H₂ to [Ir(ⁱPr-PONOP)(propene)][BAr^F₄] and Comparison Between Solid-State and Solution Reactivity

Blatter Radical-Decorated Silica as a Prospective Adsorbent for Selective NO Capture from Air

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NO sorption, in-crystal nitrite and nitrate production with arylamine oxidation in gas–solid single crystal to single crystal reactions

Abstract: Chemisorptive capture and in-crystal conversions of NO at dicobalt site SC–SC reactions.

Cited by 4 publications

References 21 publications

Solid Phase Nitrosylation of Enantiomeric Cobalt(II) Complexes

Solid Phase Nitrosylation of Enantiomeric Cobalt(II) Complexes

Single-Crystal to Single-Crystal Addition of H2 to [Ir(iPr-PONOP)(propene)][BArF4] and Comparison Between Solid-State and Solution Reactivity

Blatter Radical-Decorated Silica as a Prospective Adsorbent for Selective NO Capture from Air

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Single-Crystal to Single-Crystal Addition of H₂ to [Ir(ⁱPr-PONOP)(propene)][BAr^F₄] and Comparison Between Solid-State and Solution Reactivity