Highly efficient photometathesis in a proximate, synperiplanar diazene-diazene oxide substrate: retention of optical purity, mechanistic implications

Exner, Kai S.; Prinzbach, Horst

doi:10.1039/a709232f

Cited by 7 publications

(3 citation statements)

References 13 publications

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“…A conceivable photo-cycloaddition synthetic strategy was proposed by introducing rigid bisazo scaffolds 14 , yet it has been proven unsuccessful due to the propensity of N 2 extrusion 15 . To this end, a substituted tetrazetidine radical cation [N 4 (CO 2 -i Pr) 4 ] •+ was detected in solution by electron paramagnetic resonance (EPR) spectroscopy upon oxidation 16 .…”

Section: Introductionmentioning

confidence: 99%

Capturing a Tetratomic Nitrogen Ring cyclo-N4 inside an Aza[ 82 ]fullerene

Wang

Shen

et al. 2021

Preprint

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Synthesis of polymeric nitrogen compounds is a formidable task due to the proneness of nitrogen to the formation of N ≡ N triple bond, one of the strongest chemical bonds known. Here, we report an arc-discharge approach to successfully stabilize the elusive four-membered nitrogen ring (cyclo-N4) in an unprecedented endohedral metallofullerene Dy2N4@C81N (Dy-I). Its molecular structure has been unambiguously determined by X-ray crystallography to show a covalently bonded cyclo-N4 plane bridging two dysprosium ions inside an aza[82]fullerene cage, highlighting the stabilization of cyclo-N4 as a concurrent result of fullerene encapsulation and metal coordination. Our computational results further reveal a six-center-one-electron (6c-1e) bond delocalized over the inverse-sandwich Dy-N4-Dy cluster. This chemical peculiarity stems from the diffuse radical character of the highly anionic cyclo-N43− ligand, which is confirmed by electron paramagnetic resonance (EPR) spectrum of Y2N4@C81N (Y-I).

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Section: Introductionmentioning

confidence: 99%

Capturing a Tetratomic Nitrogen Ring cyclo-N4 inside an Aza[ 82 ]fullerene

Wang

Shen

et al. 2021

Preprint

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“…One year later, Hansen and Wodtke reported the first evidence for the production of a ring isomer of N 3 , which is confirmed by later experimental − and theoretical , work. The synthesis of the N 4 ring was attempted as early as 1982 through a (2 + 2) cycloaddition reaction, − but it was not until 2012 that Camp and co-workers detected a tetraalkyl tetrazetidinetetracarboxylate radical cation, which was the first discovery of a substituted N 4 ring in experiment as far as we know.…”

Section: Introductionmentioning

confidence: 99%

Mass Spectrometry and Theoretical Investigation of VN_n⁺ (n = 8, 9, and 10) Clusters

Ding¹,

Yang

et al. 2018

J. Phys. Chem. A

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VN clusters were generated by laser ablation and analyzed by mass spectrometry. The results showed that VN, VN, and VN clusters were formed, and the mass peak of VN is dominant in the spectrum. The VN cluster was further investigated by a photodissociation experiment with 266 nm photons. Density functional theory calculations were conducted at the M06-2X/6-311+G(d,p) level to search for stable structures of VN ( n = 8, 9, and 10) and their neutral counterparts. The theoretical calculations revealed that the most stable structure of VN is in the form of V(N) with D symmetry. The binding energy from the calculation is in good agreement with that obtained from the photodissociation experiments. The global minimum structures of VN, VN, and VN contain a similar substructure of the N ring and exhibit energy properties. The most stable structure of VN is in the form of (η-N)VN(N) with C symmetry, while that of VN is in the form of (η-N)V(N) with C symmetry. For neutral VN, VN, and VN, (η-N)V(N), (η-N)V(N)(N), and (η-N)V(N) are their ground-state structures, with decomposition into one V atom, and corresponding quantities of N can release energies of about 50.20, 96.28, and 57.76 kcal/mol, respectively.

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“…Arguments have been put forward for why cycloaddition could not compete with more or less rapid N 2 elimination even in the most promising, near to perfectly syn-periplanar, A-systems. [10,11] One such argument was based on the fact that exothermic metathetical isomerization into the B-type isomers, via the respective tetrazetidine N-Oxides as vibrationally excited transients, [12] might become a highly competitive process after N-oxidation of A-type bis(diazenes). [1,13] In contrast, various B-, [13] C-, [14] and D-type N-Oxides, [15] in which metathesisis significantly endothermic, underwent only standard photoprocesses (deoxygenation, oxaziridine formation).…”

Section: Introductionmentioning

confidence: 99%

Proximate, “Parallel‐In‐Plane” Preoriented Bis(diazenes) − In‐Plane Delocalized Bis(homoconjugated) 4N/5(6)e Anions

et al. 2003

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Synthetic details are presented for a series of more or less rigid, “parallel‐in‐plane” preoriented bis(diazenes), with N=N/N=N distances (d) of 3.3−2.9 Å and interorbital angles (ψ) of 142−164° (X‐ray crystal structures). DFT calculations (B3LYP/6−31G*) and one‐/two‐electron reduction experiments with the two least preoriented, most “distant” bis(diazenes) (dN=N/N=N ca. 3.3 Å; ψ 142−146°) provide more insight into the structural prerequisites for bis(homoconjugative) in‐plane electron delocalization in 4N/5e radical anions and 4N/6e dianions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Highly efficient photometathesis in a proximate, synperiplanar diazene-diazene oxide substrate: retention of optical purity, mechanistic implications

Cited by 7 publications

References 13 publications

Capturing a Tetratomic Nitrogen Ring cyclo-N4 inside an Aza[ 82 ]fullerene

Capturing a Tetratomic Nitrogen Ring cyclo-N4 inside an Aza[ 82 ]fullerene

Mass Spectrometry and Theoretical Investigation of VN_n⁺ (n = 8, 9, and 10) Clusters

Proximate, “Parallel‐In‐Plane” Preoriented Bis(diazenes) − In‐Plane Delocalized Bis(homoconjugated) 4N/5(6)e Anions

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Highly efficient photometathesis in a proximate, synperiplanar diazene-diazene oxide substrate: retention of optical purity, mechanistic implications

Cited by 7 publications

References 13 publications

Capturing a Tetratomic Nitrogen Ring cyclo-N4 inside an Aza[ 82 ]fullerene

Capturing a Tetratomic Nitrogen Ring cyclo-N4 inside an Aza[ 82 ]fullerene

Mass Spectrometry and Theoretical Investigation of VNn+ (n = 8, 9, and 10) Clusters

Proximate, “Parallel‐In‐Plane” Preoriented Bis(diazenes) − In‐Plane Delocalized Bis(homoconjugated) 4N/5(6)e Anions

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Mass Spectrometry and Theoretical Investigation of VN_n⁺ (n = 8, 9, and 10) Clusters