cis-Azoxyalkanes. III. Dichotomy in the thermal stability of azo- and azoxyalkanes

Snyder, James P.; Lee, Ling; Bandurco, Victor T.; Yu, Chunyang; Boyd, Russell J.

doi:10.1021/ja00764a075

Cited by 24 publications

(9 citation statements)

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“…1 H NMR (400 MHz, CDCl 3 , 293 K): δ =6.56–6.51 (m, 2 H, vinyl‐CH), 5.39–5.34 (m, 2 H, bridgehead CH), 2.07–2.00 (m, 1 H, bridge‐CH 2 ), 1.92–1.85 (m, 1 H, bridge‐CH 2 ), 1.67–1.60 (m, 1 H, bridge‐CH 2 ), 1.55–1.49 ppm (br t, 1 H, bridge‐CH 2 ); 13 C NMR (100 MHz, CDCl 3 , 293 K): δ =132.0, 128.6, 74.0, 60.3, 23.4, 21.7 ppm; FTIR (ATR): $\tilde \nu $ =1496 cm −1 (N‐ N ‐O); HRMS (ESI): m / z : calcd for C 6 H 8 N 2 O: 163.0268 [ M +K + ], 147.0529 [ M +Na + ], 125.0709 [ M +H + ], 249.1346 [ M 2 +H + ], 271.1165 [ M 2 +Na + ]; found: 163.0275, 147.0526, 125.0718, 249.1362, 271.1163. 1 H NMR chemical shift ranges30b,e, 47 and 13 C NMR30c data agree with those in the literature.…”

Section: Methodssupporting

confidence: 90%

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Solvothermal Reactions between Barium, Manganese, and Tellurium in Methylamine – the Formation of Polytellurides and Unexpected Cyanido Complexes

Kysliak

Beck

2013

Zeitschrift anorg allge chemie

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The reactions between elemental barium or manganese and tellurium in methylamine under solvothermal conditions at temperatures between 50 and 100 °C yield the tri‐ and ditellurides [Ba(MeNH2)3]Te3 (1) and [Mn(MeNH2)4Te2]n (2). The analogous reactions with mixtures of both metals barium and manganese lead additionally to cyanide‐containing species [Mn2(MeNH2)9(μ‐CN)(Te2)]2(Te2) (3) and [Mn2(MeNH2)10(μ‐CN)]2(Te3)3·4MeNH2 (4). Under solvothermal conditions in the presence of metallic barium and manganese methylamine partially undergoes dehydrogenation being converted to cyanide ions. In the structure of 1, Ba2+ is coordinated by three MeNH2 ligands and five tellurium atoms of surrounding Te32– anions, which are associated to infinite (Te32–)n polyanionic chains. 2 is a coordination polymer with Mn(MeNH2)4 groups connected by Te2 units to chains [Te–Te–Mn–]n. 3 and 4 are molecular compounds, consisting of cationic dinuclear complexes with almost linear Mn2+–CN–Mn2+ bridges. In the structures 2–4 manganese is in octahedral coordination.

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Section: Methodssupporting

confidence: 90%

“…Bicyclic azoxyalkanes (N‐oxides) are remarkably more stable than their deoxy relatives; for example, the azoalkene 17 generated at −78 °C rapidly decomposes to 1,3‐cyclohexadiene and nitrogen even at this low temperature 31. On the other hand, 16 resists thermal change below 175 °C 30b…”

Section: Resultsmentioning

confidence: 99%

Solvothermal Reactions between Barium, Manganese, and Tellurium in Methylamine – the Formation of Polytellurides and Unexpected Cyanido Complexes

Kysliak

Beck

2013

Zeitschrift anorg allge chemie

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“…As previous we have taken advantage of the great stability of azo-A-oxides to prepare several new systems with hydrocarbon backbones inaccessible in the azo series.8 Hydrolytic oxidation of cycloadduct 5 with strongly basic hydrogen peroxide1•6 generates compound 6 (mp 48-50°, 50% yield) in a single step.9 A-Oxides 7 (mp 101-102°, 65%) and 8 (mp 119-120°, 80%) arise similarly as outlined in Scheme I.…”

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cis-Azoxyalkanes. V. Concerted retrocycloaddition of nitrous oxide

Olsen¹,

Snyder²

1974

J. Am. Chem. Soc.

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with those in the spectrum of the equimolar mixture (see footnote a to Table I for assignments) then points clearly to the contributions from CrmCl6 and Mo'^Cle chromophores in the spectrum of CrMoClg3-. This information makes it equally clear that reaction 3 involves electron transfer. Furthermore, the electronic spectrum of CrMoClg3is in full accord with a confacial, bioctahedral structure since this structure is the only one which will simultaneously accommodate both CrulCl6 and MoulCl6 chromophores. Finally, the magnetic moment per formula unit of [(«-C4H9)4N]3CrMoClg is 4.38 BM at 295°K and 3.10 BM at 77°K. These results are in accord with antiferromagnetic coupling between the two S = % spin systems.The only other dinuclear or polynuclear species containing both chromium and molybdenum is the Cr(II)-Mo(II)acetate compound, CrMo(OAc)4, which was recently prepared.6Acknowledgment. Financial aid from the National Science Foundation (Grant No. GP-30544X) is acknowledged. References and Notes(1) W.

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“…A plausible explanation is offered based upon perturbation of the orbital energies of the azo linkage by the ^N -> 0 dative bond of the azoxy structure (Snyder et al, 1972a). A plausible explanation is offered based upon perturbation of the orbital energies of the azo linkage by the ^N -> 0 dative bond of the azoxy structure (Snyder et al, 1972a).…”

Section: (16)mentioning

confidence: 99%

Cheletropic Reactions

Mock¹

1977

Organic Chemistry: A Series of Monographs

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cis-Azoxyalkanes. III. Dichotomy in the thermal stability of azo- and azoxyalkanes

Cited by 24 publications

References 1 publication

Solvothermal Reactions between Barium, Manganese, and Tellurium in Methylamine – the Formation of Polytellurides and Unexpected Cyanido Complexes

Solvothermal Reactions between Barium, Manganese, and Tellurium in Methylamine – the Formation of Polytellurides and Unexpected Cyanido Complexes

cis-Azoxyalkanes. V. Concerted retrocycloaddition of nitrous oxide

Cheletropic Reactions

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