First Identification of an Aliphatic cis-α,β-Dinitroso Compound:  A Combined Experimental and Quantum Chemical Study

Himmel, Hans‐Jörg; Konrad, Serge; Friedrichsen, Willy; Rauhut, Guntram

doi:10.1021/jp0341117

Cited by 8 publications

(9 citation statements)

References 27 publications

(45 reference statements)

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“…The exceptional stability of these furoxan-like heterocycles with respect to hydrolysis and UV irradiation 108 elevates their potential importance in atmospheric chemistry because they may ultimately be organic nitrogen sinks in the atmosphere. For example, photolysis of benzofuroxan (l = 366 nm) 109,110 and 3,4-dimethylfuroxan (l = 254 nm) 111 produces the shortlived dinitroso intermediate that both thermally and photochemically regenerates the heterocycle. Comparatively, other photoproducts like carbonyls and nitro compounds are much more photolabile.…”

Section: Mechanism Of Formation For Nocmentioning

confidence: 99%

Direct aqueous photochemistry of isoprene high-NOx secondary organic aerosol

Nguyen

Laskin

et al. 2012

Phys. Chem. Chem. Phys.

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Secondary organic aerosol (SOA) generated from the high-NO(x) photooxidation of isoprene was dissolved in water and irradiated with λ > 290 nm radiation to simulate direct photolytic processing of organics in atmospheric water droplets. High-resolution mass spectrometry was used to characterize the composition at four time intervals (0, 1, 2, and 4 h). Photolysis resulted in the decomposition of high molecular weight (MW) oligomers, reducing the average length of organics by 2 carbon units. The average molecular composition changed significantly after irradiation (C(12)H(19)O(9)N(0.08) + hν → C(10)H(16)O(8)N(0.40)). Approximately 65% by count of SOA molecules decomposed during photolysis, accompanied by the formation of new products. An average of 30% of the organic mass was modified after 4 h of direct photolysis. In contrast, only a small fraction of the mass (<2%), belonging primarily to organic nitrates, decomposed in the absence of irradiation by hydrolysis. Furthermore, the concentration of aromatic compounds increased significantly during photolysis. Approximately 10% (lower limit) of photodegraded compounds and 50% (upper limit) of the photoproducts contain nitrogen. Organic nitrates and multifunctional oligomers were identified as compounds degraded by photolysis. Low-MW 0N (compounds with 0 nitrogen atoms in their structure) and 2N compounds were the dominant photoproducts. Fragmentation experiments using tandem mass spectrometry (MS(n), n = 2-3) indicate that the 2N products are likely heterocyclic/aromatic and are tentatively identified as furoxans. Although the exact mechanism is unclear, these 2N heterocyclic compounds are produced by reactions between photochemically-formed aqueous NO(x) species and SOA organics.

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Section: Mechanism Of Formation For Nocmentioning

confidence: 99%

Direct aqueous photochemistry of isoprene high-NOx secondary organic aerosol

Nguyen

Laskin

et al. 2012

Phys. Chem. Chem. Phys.

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“…Firstly, as noted earlier, direct spectroscopic identification of such species in ring opening and/or tautomerism of monocyclic disubstituted furoxans are rare, most attention having been given to tautomerism processes in benzofuroxans. 18 Recently, formation and identification (FTIR) of dimethyldinitrosoethylene (2,3-dinitrosobut-2-ene), from photolysis of dimethylfuroxan in an argon matrix at 12 K has been demonstrated, 31 with RB3LYP/cc-pVTZ calculations favouring the tct isomer (of the four conformers, tct, ctc, ctt and ttt located) as the species generated in the matrix. The present results suggest a possible re-evaluation; re-calculation of all structures of ref.…”

Section: Dimerisation To Furoxansmentioning

confidence: 99%

“…The tautomerism process involving dimethylfuroxan, which was investigated theoretically (B3LYP) and experimentally (FTIR), identified the presence of dinitrosoethylene species. 31 Much of this early work, however, must be viewed with some caution since it involved restricted wave functions and possible open-shell (singlet diradical) structures were not considered. More recently the intermediates calculated (UB3LYP) in the step-wise dimerisation of HCRCCNO were found to have open-shell singlet structures, 32 and UB3LYP calculations for CH 3 CNO and ClC 6 H 5 CNO dimerisation 25,33 showed a step-wise process involving dinitrosoalkene intermediates with considerable diradical character.…”

Section: Introductionmentioning

confidence: 99%

Dimerisation of nitrile oxides: a quantum-chemical study

Pasinszki

Hajgató

Havasi

et al. 2009

Phys. Chem. Chem. Phys.

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The [3 + 2] and [3 + 3] cyclodimerisation processes of small nitrile oxides, XCNO (X = F, Cl, Br, CN, CH(3)) are investigated by ab initio coupled cluster theory at the CCSD, CCSD(T) and MR-AQCC levels for the first time. The favoured dimerisation process is a multi-step reaction to furoxans (1,2,5-oxadiazole-2-oxides) involving dinitrosoalkene-like intermediates with diradical character. The rate determining step for all but the F-species is the first, corresponding to the C-C bond formation. The kinetic energy barrier depends on the nature of the substituent X, generally increasing with decreasing electronegativity and increasing pi-donor ability of the substituent: F (DeltaG(298) = 0 kJ mol(-1)) < Cl (72) < Br (90) < CH(3) (104) < CN (114) (MR-AQCC(2,2)//UB3LYP/cc-pVTZ). Following initial C-C bond formation, three possible dinitrosoethylene diradical pathways are explored. Two of them are new, and one of them is a low-energy three-step path with implications for cycloreversion, tautomerism and detection of dinitrosoethylene intermediates. Alternative one-step, concerted [3 + 2] and [3 + 3] cyclodimerisation processes leading to 1,2,4-oxadiazole-4-oxides and 1,4,2,5-dioxadiazines have kinetic energy barriers around 100-240 kJ mol(-1) (CCSD//B3LYP), some 1.6 to 2.5 times higher than those leading to furoxans, supporting the experimental observations of furoxan formation as nitrile oxide loss channels during storage, trapping/re-vaporisation and reactions of nitrile oxides. Potential polymerisation initiation processes for NCCNO, involving the 1,2-dipolar NC substituent are also explored.

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“…Other papers on ab initio calculations for 1,2-dinitrosoethylene at different levels of computation have been published. [118][119][120][121][122][123][124] Interestingly, IR spectroscopic evidence for the formation of 2,3-dinitrosobut-2-ene as the photolabile intermediate during UV photolytic decomposition of dimethylfuroxan has been obtained, 124 and the product was identified as the tct-2,3-DNB conformer with the help of theoretical calculations.…”

Section: Theoretical Studies Of Dinitroso Compoundsmentioning

confidence: 99%

Dinitroso and polynitroso compounds

Gowenlock

Richter‐Addo

2005

Chem. Soc. Rev.

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The growing interest in the chemistry of C-nitroso compounds (RN=O; R = alkyl or aryl group) is due in part to the recognition of their participation in various metabolic processes of nitrogen-containing compounds. C-Nitroso compounds have a rich organic chemistry in their own right, displaying interesting intra- and intermolecular dimerization processes and addition reactions with unsaturated compounds. In addition, they have a fascinating coordination chemistry. While most of the attention has been directed towards C-nitroso compounds containing a single -NO moiety, there is an emerging area of research dealing with dinitroso and polynitroso compounds. In this critical review, we present and discuss the synthetic routes and properties of these relatively unexplored dinitroso and polynitroso compounds, and suggest areas of further development involving these compounds. (126 references.).

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First Identification of an Aliphatic cis-α,β-Dinitroso Compound: A Combined Experimental and Quantum Chemical Study

Cited by 8 publications

References 27 publications

Direct aqueous photochemistry of isoprene high-NOx secondary organic aerosol

Direct aqueous photochemistry of isoprene high-NOx secondary organic aerosol

Dimerisation of nitrile oxides: a quantum-chemical study

Dinitroso and polynitroso compounds

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