Direct Observation of a Photoinduced Nonstabilized Nitrile Imine Structure in the Solid State

Zheng, Shao‐Liang; Wang, Yizhong; Yu, Zhipeng; Lin, Qing; Coppens, Philip

doi:10.1021/ja9094523

Cited by 64 publications

(49 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The MS 2 spectrum of Compound 3 is collected in Figure 1 showing the molecular ion at m/z 938.9 and the fullerene radical ion at m/z 720.0 together with the proposed mechanism for this elimination. Although there are different proposed structural possibilities to describe the nitrile imine, we use the 1,3-dipolar structure because recent investigations demonstrate that the nitrile imine is the major structure involved in the 1,3-dipolar cycloaddition reactions [39]. No differences were found for the alkyl substituents attached at the C3 position of the heterocyclic ring.…”

Section: Resultsmentioning

confidence: 99%

Mass Spectrometry Studies of the Retro-Cycloaddition Reaction of Pyrrolidino and 2-Pyrazolinofullerene Derivatives Under Negative ESI Conditions

Delgado

Filippone

Martín‐Domenech

et al. 2011

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

Substituted pyrrolidino-and 3-alkyl-2-pyrazolinofullerenes ionize under ESI and MALDI mass spectrometry conditions and negative mode of detection undergoing mass spectral fragmentations, which can be easily correlated with the reported results for the thermal and electrochemical retro-cycloaddition reactions of these compounds. 2-Pyrazolinofullerenes lead directly to a [60] fullerene product ion formed through a retro-cycloaddition process regardless of the substituents attached at the carbon and nitrogen atoms of the heterocyclic ring. These results are different from whose reported for the thermal and electrochemical processes. In contrast, pyrrolidinofullerenes undergo different fragmentative reactions depending upon the substituents (hydrogen, alkyl, or acyl) attached at the nitrogen atom of the heterocyclic ring leading eventually to the pristine C 60 in the last step of the fragmentation pathway.

show abstract

Section: Resultsmentioning

confidence: 99%

Mass Spectrometry Studies of the Retro-Cycloaddition Reaction of Pyrrolidino and 2-Pyrazolinofullerene Derivatives Under Negative ESI Conditions

Delgado

Filippone

Martín‐Domenech

et al. 2011

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

show abstract

“…When tetrazoles are irradiated with UV light, a nitrile imine is formed which can subsequently complete a cycloaddition with olefins present in situ (Zheng et al, 2009). After cycloaddition, a fluorescent pyrazoline is produced that can be used as a tag to monitor product formation.…”

Section: Structure Descriptionmentioning

confidence: 99%

Ammonium hydrogen bis[4-(2-phenyl-2H-tetrazol-5-yl)benzoate]

Janzen¹,

Lange²,

Wollack³

2016

IUCr Data

View full text Add to dashboard Cite

The title salt, NH4 +·H+·2C14H9N4O2 −, is composed of an ammonium cation with a strong intermolecular negatively charge-assisted hydrogen-bonded acid/conjugate base-pair monoanion. The carboxylic acid H atom is located on an inversion center, while the N atom of the ammonium cation is located on a twofold rotation axis. In the crystal, the N—H bonds of each ammonium cation act as donors with carboxylate O-atom acceptors to form chains along the a-axis direction. The chains are linked by offset π–π interactions [intercentroid distances = 3.588 (2) and 3.686 (2) Å], forming layers parallel to the ab plane.

show abstract

“…Sufficient elasticity of voids can also be beneficial [6][7][8]. The occurrence of a photochemical reaction was explained in some cases by the analysis of size and shape of voids: a big void promoted the reaction [9][10][11], whereas one that is too small hindered it [12].…”

Section: Introductionmentioning

confidence: 99%

Structural Transformations in Crystals Induced by Radiation and Pressure. Part 7. Molecular and Crystal Geometries as Factors Deciding about Photochemical Reactivity under Ambient and High Pressures

et al. 2018

View full text Add to dashboard Cite

Abstract:We studied the photochemical reactivity of salts of 4-(2,4,6-triisopropylbenzoyl)benzoic acid with propane-1,2-diamine (1), methanamine (2), cyclohexanamine (3), and morpholine (4), for compounds (1), (3), and (4) at 0.1 MPa and for compounds (1) and (2) at 1.3 GPa and 1.0 GPa, respectively. The changes in the values of the unit cell parameters after UV irradiation and the values of the intramolecular geometrical parameters indicated the possibility of the occurrence of the Norrish-Yang reaction in the case of all the compounds. The analysis of the intramolecular geometry and free spaces revealed which o-isopropyl group takes part in the reaction. For (1), the same o-isopropyl group should be reactive at ambient and high pressures. In the case of (2), high pressure caused the phase transition from the space group I2/a with one molecule in the asymmetric unit cell to the space group P1 with two asymmetric molecules. The analysis of voids indicated that the Norrish-Yang reaction is less probable for one of the two molecules. For the other molecule, the intramolecular geometrical parameters showed that except for the Norrish-Yang reaction, the concurrent reaction leading to the formation of a five-membered ring can also proceed. In (3), both o-isopropyl groups are able to react; however, the bigger volume of a void near 2-isopropyl may be the factor determining the reactivity. For (4), only one o-isopropyl should be reactive.

show abstract

Direct Observation of a Photoinduced Nonstabilized Nitrile Imine Structure in the Solid State

Cited by 64 publications

References 22 publications

Mass Spectrometry Studies of the Retro-Cycloaddition Reaction of Pyrrolidino and 2-Pyrazolinofullerene Derivatives Under Negative ESI Conditions

Mass Spectrometry Studies of the Retro-Cycloaddition Reaction of Pyrrolidino and 2-Pyrazolinofullerene Derivatives Under Negative ESI Conditions

Ammonium hydrogen bis[4-(2-phenyl-2H-tetrazol-5-yl)benzoate]

Structural Transformations in Crystals Induced by Radiation and Pressure. Part 7. Molecular and Crystal Geometries as Factors Deciding about Photochemical Reactivity under Ambient and High Pressures

Contact Info

Product

Resources

About