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26
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0242521031
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note
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Reversible formation of [2 + 2] cycloadducts for the C-/D-bis(diazenes) [and all bis(diazene) N-Oxides] cannot be rigorously ruled out. In fact, the very slow conversion of one or the other substrate is suggestive of unproductive consumption of light.
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28
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8]THF, see Figure 14 in ref.[18a]) are reasonably well reproduced by the B3LYP/6-31G* calculations (513.0 or 293.8 ppm; Δ¡ = 219.2 ppm).[2g] For the recent generation of 4N/6e dianions by oxidation of the corresponding (presumably) bislithiated bis(hydrazines) and of 4N/6e monoanions through addition of organometallic reagents to A-type bis(diazenes)
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2-symmetrical bisanion); [2g] α-peralkylated analogues could not be constructed. For azine bridges as conjugation stoppers see: P. Zuman, J. Ludvik, Tetrahedron Lett. 2000, 41, 7851-7853. M. Lewis, R. Glaser, J. Org Chem. 2002,. 67, 1441-1447. EQUATION PRESENTATION
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2-symmetrical bisanion); [2g] α-peralkylated analogues could not be constructed. For azine bridges as conjugation stoppers see: P. Zuman, J. Ludvik, Tetrahedron Lett. 2000, 41, 7851-7853. M. Lewis, R. Glaser, J. Org Chem. 2002,. 67, 1441-1447. EQUATION PRESENTATION
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[c] K. Exner, B. Großmann, G. Gescheidt, J. Heinze, M. Keller, T. Bally, P. Bednarek, H. Prinzbach, Angew. Chem. 2000, 112, 1514-1517; Angew. Chem. Int. Ed. 2000, 39, 1455-1458.
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note
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2, d = 4.75 Å} σ complexes had resulted.[23a]
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48
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[b] For a comparison of experimentally measured and calculated geometries of sesquibicyclic hydrazines, see: S. F. Nelsen, Y. Wang, D. R. Powell, R. K. Hayashi, J Am. Chem. Soc. 1993, 115, 5246-5253.
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0242689797
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note
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Once various B-type bis(diazene) N-oxides had become available as photoproducts of their A-type isomers,[13] their deoxygenation seemed a convenient route to the respective bis(diazenes). In line with literature reports, [14] however, strain-related complications made this approach impractical.
-
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50
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0000859155
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[a] N. Bahr, E. Beckmann, K. Mathauer, D. Hunkler, M. Keller, H. Prinzbach, H. Vahrenkamp, Chem. Ber. 1993, 126, 429-440.
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[b] C. f. G. Fischer, G. Sedelmeier, H. Prinzbach, K. Knoll, P. Wilharm, G. Huttner, J. Organomet. Chem. 1975, 297, 307-312.
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0242605784
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note
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The intricacies of the multistep hydrazine reaction were once more evident when under the conditions of the neat transformation 1b → 3b the respective 2,8-dione[24] delivered only polymers.
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CCDC ref. codes KEMGUE (20),[36] 188159 (34a), 188160 (34d), and 188162 (33d) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.) +44-1223-336-033; E-mail: deposit@ccdc.cam.ac.uk].
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Calculation of these geometries with the B3LYP functional, irrespective of its inherent deficiency when it comes to localization of spin and/or charge (T. Bally, G. N. Sastry, J. Phys. Chem. A, 1997, 101, 7923-7925), has been justified, see ref. [2h, [8a]
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The value 1.29 given in ref.[18a] needs to be corrected
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The value 1.29 given in ref.[18a] needs to be corrected.
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101
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0242689801
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manuscript to be published
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M. Heizmann, F. Yang, M. Kegel, K. Exner, H.-D. Beckhaus, M. Keller, L. Knothe, B. Großmann, J. Heinze, H. Prinzbach, manuscript to be published.
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