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41
-
-
13044267386
-
-
note
-
In this experiment, cyclobuta[de]naphthalene (4) is detectable only by UV/visible spectroscopy (Figure 2). The concentration of 4 in the matrix remains constant throughout subsequent photolyses.
-
-
-
-
42
-
-
13044251499
-
-
note
-
Information available as Supporting Information.
-
-
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43
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0001440236
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13044295684
-
-
note
-
max 343 nm) is consistent with Horn's description.
-
-
-
-
46
-
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0000448891
-
-
For leading references, see: (a) McMahon, R. J.; Chapman, O. L.; Hayes, R. A.; Hess, T. C.; Krimmer, H. P. J. Am. Chem. Soc. 1985, 107, 7597-7606. (b) Reference 1e, p 311.
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McMahon, R.J.1
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47
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Reference 1e, p 311
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For leading references, see: (a) McMahon, R. J.; Chapman, O. L.; Hayes, R. A.; Hess, T. C.; Krimmer, H. P. J. Am. Chem. Soc. 1985, 107, 7597-7606. (b) Reference 1e, p 311.
-
-
-
-
50
-
-
13044270662
-
-
note
-
The ratio of s-E:s-Z rotamers remains constant as observed by ESR spectroscopy. Additionally, all infrared bands attributed to 1 appear and disappear at the same rate.
-
-
-
-
51
-
-
13044305546
-
-
note
-
max resulting from the overlapping absorption spectra of the two conformers. We attempted the analogous experiment with our system (λ = 356 ± 10 nm). In this instance, however, the ratio of s-E:s-Z isomers of carbene 1 did not change.
-
-
-
-
53
-
-
13044295685
-
-
note
-
The subtle spectral changes are difficult to observe by infrared spectroscopy. Very few bands can be distinguished from the baseline and only the steady disappearance of 4 can be tracked with certainty.
-
-
-
-
54
-
-
13044293685
-
-
note
-
Because cyclobuta[de]naphthalene (4) was prepared by flash vacuum pyrolysis of 1-naphthyldiazirine (12), we speculated that a trace amount of diazirine contaminant in the matrix could be responsible for the ESR signal observed on photolysis of 4. However, extended photolysis (λ = 396 ± 10 nm) of 4 under conditions where diazirine 12 is known to afford triplet 1-naphthylcarbene (1) failed to produce the triplet ESR signal of carbene 1.
-
-
-
-
55
-
-
13044290313
-
-
note
-
max 484, 416, 327, 316, 298, 284 nm). Further irradiation (λ > 200, λ = 290 ± 10 or λ > 300 nm) produces no discernible change. The spectroscopic bands do not decay in the dark at 10 K, even over several hours. Full arc irradiation (λ > 200 nm) of 4 followed by broad-band photolysis (λ > 497 nm) results in complete disappearance of the 912 G ESR signal as well as the expected disappearance of carbene 1. The 912 G signal can be partially regenerated by photolyzing at λ = 290 ± 10 nm or completely regenerated by full arc irradiation. The intensity of the other ESR signals (648, 1456, 1670 G) does not change under any of the photochemical conditions.
-
-
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56
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0032546303
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13044262826
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2〉 = 0.
-
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65
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0031801543
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13044287037
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note
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The ratio of matrix to sample is always approximately 500:1.
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13044292311
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NMR and mass spectral characterization are complicated by the compound's insolubility in a wide variety of solvents.
-
-
-
|