Tetrazetidine: ab initio calculations and experimental approach

Ritter, G.; Haefelinger, G.; Lueddecke, E.; Rau, Hermann

doi:10.1021/ja00195a016

Cited by 41 publications

(10 citation statements)

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“…This product may have a tetrazetidine structure which we have tried to hunt down for a long time. 26 However the nature of the photoproduct could not be proven, mainly for solubility reasons. So there is another hint, but the tetrazetidine ring structure still is elusive.…”

Section: Discussionmentioning

confidence: 99%

A non-rotatory isomerization path in ethene derivatives? Investigation of a stilbenophane and protonated azobenzenophanes (“pseudo-stilbenophanes”)Dedicated to Professor F. Dörr on the occasion of his 80th birthday.Electronic supplementary information (ESI) available: Synthesis of stilbenophane and protonated azobenzenophanes. See http://www.rsc.org/suppdata/cp/b1/b111483m/

Rau

Waldner

2002

Phys. Chem. Chem. Phys.

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Section: Discussionmentioning

confidence: 99%

A non-rotatory isomerization path in ethene derivatives? Investigation of a stilbenophane and protonated azobenzenophanes (“pseudo-stilbenophanes”)Dedicated to Professor F. Dörr on the occasion of his 80th birthday.Electronic supplementary information (ESI) available: Synthesis of stilbenophane and protonated azobenzenophanes. See http://www.rsc.org/suppdata/cp/b1/b111483m/

Rau

Waldner

2002

Phys. Chem. Chem. Phys.

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“…Ab initio calculations performed by Ritter et al showed that the highest occupied molecular orbital (HOMO, 16) for the neutral tetrazetidine molecule (1, R = H) with the same butterfly arrangement of nitrogen atoms described here for 5 (depicted as configuration 3a in their paper) also had D 2d symmetry with an A 1 representation that contained the lone pair of electrons. 1 Removal of an electron from the HOMO would afford a radical cation analogous to 5. Examination of the SOMO furthermore reveals significant spin density along the N-C(C=O) bond.…”

Section: Somomentioning

confidence: 99%

“…1 This investigation accompanied the attempted thermal-and photo-isomerization of diazobenzenophane in an effort to rationalize a peculiarity in the experimental results which the authors speculated could be a short-lived tetrazetidine intermediate. 1 Importantly, although the evidence for a four-membered nitrogen ring intermediate was not conclusive, the calculations nevertheless suggested that tetrazetidine was a kinetically stable molecule that might be accessed via photochemical techniques. Later structural refinements underpinned by higher level ab initio calculations indicated that the lowest energy conformation of tetrazetidine adopted a D 2d symmetry in which the four hydrogen atoms are staggered around a slightly puckered N 4 ring.…”

Section: Introductionmentioning

confidence: 99%

Formation of an Unusual Four-Membered Nitrogen Ring (Tetrazetidine) Radical Cation

et al. 2012

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Treatment of triphenylphosphine (Ph(3)P) with an excess of diisopropyl azodicarboxylate at 0-25 °C resulted in the formation of a symmetrical tetraalkyl tetrazetidinetetracarboxylate radical cation, containing the elusive cyclic N(4) ring system. Electron paramagnetic resonance (EPR) spectroscopy revealed a 9-line spectrum, with hyperfine coupling constants indicative of four almost magnetically equivalent nitrogen atoms. The radical species was surprisingly long-lived, and could still be observed several hours after generation and standing at 25 °C. Expansion of the central resonance revealed further splitting into a pentet (hyperfine coupling to the four methine protons). Three mechanistically plausible structures containing the tetrazetidine substructure were proposed based on the 9-line EPR spectrum. Following DFT calculations, the predicted hyperfine coupling constants were used to simulate the EPR spectra for the three candidate structures. The combined calculations and simulations were consistent with a radical cation species, but not a radical anion or radical-carbenoid structure. The lowest energy conformation of the N(4) ring was slightly puckered, with the alkyl carboxylate groups all trans and the four carbonyl groups aligned in a pinwheel arrangement around the ring. Analogous results were obtained with the original Mitsunobu reagents, Ph(3)P and diethyl azodicarboxylate, but not with Ph(3)P and di-tert-butyl azodicarboxylate. A mechanism is proposed based on a radical version of the Rauhut-Currier or Morita-Baylis-Hillman reactions.

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“…We have not found any systematic study of the PES of tetraziridine in the literature, and we are only aware of the paper by Ritter et al, 29 where only some of the conformers of interest were studied at the HF/6-31G** level of theory. Therefore, we will summarise briefly our results at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p)G2(MP2) level.…”

Section: Molecular Systemsmentioning

confidence: 99%

Triaziridine and tetrazetidine vs. cyclic water trimer and tetramer: A computational approach to the relationship between molecular and supramolecular conformational analysis

Alcamı́

Mó

Yáñez

et al. 2002

Phys. Chem. Chem. Phys.

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The potential energy surfaces of cyclic water trimer and tetramer, as typical examples of supramolecular systems, have been compared with those of triaziridine and tetrazetidine, which can be considered as their suitable molecular analogues. The survey was performed at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p) level of theory and includes also the monomethyl and monofluoro derivatives of both the trimer and the tetramer. This comparison leads to the conclusion that supramolecular systems, where the molecular components are held together by weak interactions, exhibit the same conformational features as the analogous molecular compounds, where the constituent atoms are held together by strong covalent bonds. More importantly, even though in the former the energy required to induce conformational rearrangements is much smaller than that needed for typical molecular systems, there is a fairly good linear relationship between both magnitudes. We have also found that this quantitative relationship can be perturbed when the through-space interactions, either repulsive or attractive, between the substituents are sufficiently strong.

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Tetrazetidine: ab initio calculations and experimental approach

Cited by 41 publications

References 1 publication

Formation of an Unusual Four-Membered Nitrogen Ring (Tetrazetidine) Radical Cation

Triaziridine and tetrazetidine vs. cyclic water trimer and tetramer: A computational approach to the relationship between molecular and supramolecular conformational analysis

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