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-
-
3CN, etc.) and decomposed slowly over several days in solution or in the solid-state (see main text for a more detailed discussion of this phenomenon). These characteristics are partially responsible for the relatively low yields of the reactions summarized in Table 3.
-
3CN, etc.) and decomposed slowly over several days in solution or in the solid-state (see main text for a more detailed discussion of this phenomenon). These characteristics are partially responsible for the relatively low yields of the reactions summarized in Table 3.
-
-
-
-
85
-
-
36849054433
-
-
Dipole moments were calculated at the B3LYP (6-31G*) level of density functional theory, as implemented in the Spartan 2004 software package (Wavefunction, Irvine, CA 92612).
-
Dipole moments were calculated at the B3LYP (6-31G*) level of density functional theory, as implemented in the Spartan 2004 software package (Wavefunction, Irvine, CA 92612).
-
-
-
-
86
-
-
36849034844
-
-
Similarly, heating toluene solutions of triazenes 6-H-H and 6-H-NO2 (see Table 6) to > 150°C afforded their respective guanidines (11 and 12, not shown) in ≥95% yields. This process was conveniently monitored using 1H NMR spectroscopy. For example, the methylene groups (NCH2) in triazenes 6 exhibit diagnostic chemical shifts at 4.0-4.5 ppm in their 1H NMR spectra; chemical shifts corresponding to the same group in their respective guanidine products were found at 3.5-3.8 ppm. Note that while the thermally-induced triazene decomposition reactions generally afforded high yields >95, of guanidine products, a side-reaction was evident. The residual mass was composed of a mixture of products that eluded NMR spectroscopic identification and could not be purified via column chromatography
-
1H NMR spectra; chemical shifts corresponding to the same group in their respective guanidine products were found at 3.5-3.8 ppm. Note that while the thermally-induced triazene decomposition reactions generally afforded high yields (>95%) of guanidine products, a side-reaction was evident. The residual mass was composed of a mixture of products that eluded NMR spectroscopic identification and could not be purified via column chromatography.
-
-
-
-
88
-
-
33745741438
-
-
(b) Huynh, H. V.; Han, Y.; Ho, J. H. H.; Tan, G. K. Organometallics 2006, 25, 3267.
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(2006)
Organometallics
, vol.25
, pp. 3267
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-
Huynh, H.V.1
Han, Y.2
Ho, J.H.H.3
Tan, G.K.4
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89
-
-
33646455324
-
-
(c) Khramov, D. M.; Boydston, A. J.; Bielawski, C. W. Org. Lett. 2006, 8, 1831.
-
(2006)
Org. Lett
, vol.8
, pp. 1831
-
-
Khramov, D.M.1
Boydston, A.J.2
Bielawski, C.W.3
-
90
-
-
33749021402
-
-
(d) Khramov, D. M.; Boydston, A. J.; Bielawski, C. W. Angew. Chem., Int. Ed. 2006, 45, 6186.
-
(2006)
Angew. Chem., Int. Ed
, vol.45
, pp. 6186
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-
Khramov, D.M.1
Boydston, A.J.2
Bielawski, C.W.3
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91
-
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33744959950
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-
(e) Gehrhus, B.; Hitchcock, P. B.; Pongtavornpinyo, R.; Zhang, L. Dalton Trans. 2006, 1847.
-
(2006)
Dalton Trans
, pp. 1847
-
-
Gehrhus, B.1
Hitchcock, P.B.2
Pongtavornpinyo, R.3
Zhang, L.4
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92
-
-
0034740397
-
-
(f) Daniele, S.; Drost, C.; Gehrhus, B.; Hawkins, S. M.; Hitchcock, P. B.; Lappert, M. F.; Merle, P. G.; Bott, S. G. J. Chem. Soc., Dalton Trans. 2001, 21, 3179.
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(2001)
J. Chem. Soc., Dalton Trans
, vol.21
, pp. 3179
-
-
Daniele, S.1
Drost, C.2
Gehrhus, B.3
Hawkins, S.M.4
Hitchcock, P.B.5
Lappert, M.F.6
Merle, P.G.7
Bott, S.G.8
-
93
-
-
1842502863
-
-
(g) Myes, T. L.; Diver, S. T.; Richard, J. P.; Rivas, F. M.; Toth, K. J. Am. Chem. Soc. 2004, 126, 4366.
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(2004)
J. Am. Chem. Soc
, vol.126
, pp. 4366
-
-
Myes, T.L.1
Diver, S.T.2
Richard, J.P.3
Rivas, F.M.4
Toth, K.5
-
94
-
-
36849092814
-
-
Although the spectroscopic signatures of the resulting triazenes were in accord with the aforementioned triazenes, one notable exception was found. Signals attributable to the methylene groups of the N-iso-butyl substituents (NCH2) in triazene 6-H-H appeared as two doublets at 3.97 ppm and 4.16 ppm in its 1H NMR spectrum (solvent, CDCl3) and were tentatively assigned to cis and trans diazo (N=N) isomers, respectively. While geometric isomers often absorb radiation to differing degrees see: Hartley, G. S. J. Chem. Soc. 1938, 633
-
3) and were tentatively assigned to cis and trans diazo (N=N) isomers, respectively. While geometric isomers often absorb radiation to differing degrees (see: Hartley, G. S. J. Chem. Soc. 1938, 633
-
-
-
-
95
-
-
4644324133
-
-
max = 367 nm that was similar in shape to the triazenes discussed above (i.e., 1). This result suggested that the absorption of radiation was concomitant with geometric isomerization (i.e., cis → trans).
-
max = 367 nm that was similar in shape to the triazenes discussed above (i.e., 1). This result suggested that the absorption of radiation was concomitant with geometric isomerization (i.e., cis → trans).
-
-
-
-
96
-
-
36849043031
-
-
A similar observation was observed in benzothiazole-based triazenes analogous to 6-H-H where it was determined that cis → trans isomerization was facilitated with λ = 405 nm radiation see: Dorsch, H.-T.; Hoffman, H.; Hansel, R.; Rasch, G.; Fanghänel, E. J. Prakt. Chem. 1976, 318, 671
-
A similar observation was observed in benzothiazole-based triazenes analogous to 6-H-H where it was determined that cis → trans isomerization was facilitated with λ = 405 nm radiation (see: Dorsch, H.-T.; Hoffman, H.; Hansel, R.; Rasch, G.; Fanghänel, E. J. Prakt. Chem. 1976, 318, 671
-
-
-
-
97
-
-
36849072328
-
-
1H NMR spectroscopy. Considering density functional theory calculations at the B3LYP (6-31G**) level of theory suggested that trans 6-H-H was more stable than its eis isomer by 5.1 kcal/mol, the trans isomer was assumed to dominate in all of the triazenes prepared in this study (DFT calculations were performed using Spartan 2004, Wavefunction, Irvine, CA 92612).
-
1H NMR spectroscopy. Considering density functional theory calculations at the B3LYP (6-31G**) level of theory suggested that trans 6-H-H was more stable than its eis isomer by 5.1 kcal/mol, the trans isomer was assumed to dominate in all of the triazenes prepared in this study (DFT calculations were performed using Spartan 2004, Wavefunction, Irvine, CA 92612).
-
-
-
-
98
-
-
33750044837
-
-
For a direct comparision of N-heterocyclic carbenes with phosphines in various applications, see: a
-
For a direct comparision of N-heterocyclic carbenes with phosphines in various applications, see: (a) Rogers, M. M.; Stahl, S. S. Top. Organomet. Chem. 2007, 21, 21.
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(2007)
Top. Organomet. Chem
, vol.21
, pp. 21
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Rogers, M.M.1
Stahl, S.S.2
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100
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4544385916
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(c) Zuo, G.; Louie, J. Angew. Chem., Int. Ed. 2004, 43, 2277.
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(2004)
Angew. Chem., Int. Ed
, vol.43
, pp. 2277
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Zuo, G.1
Louie, J.2
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101
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33747838604
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(a) Shalimov, A. A.; Malenko, D. M.; Repina, L. A.; Sinitsa, A. D. Russ. J. Org. Chem. 2005, 75, 1376.
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(2005)
Russ. J. Org. Chem
, vol.75
, pp. 1376
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Shalimov, A.A.1
Malenko, D.M.2
Repina, L.A.3
Sinitsa, A.D.4
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103
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0018635779
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(c) Blum, J.; Yona, I.; Tsaroom, S.; Sasson, Y. J. Org. Chem. 1979, 44, 4178.
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(1979)
J. Org. Chem
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, pp. 4178
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Blum, J.1
Yona, I.2
Tsaroom, S.3
Sasson, Y.4
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104
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36849093871
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15N-labeled azides see: Leseticky, L.; Barth, R.; Nemec, I.; Sticha, M.; Tislerova, I. Czech. J. Phys. 2003, 53, A777.
-
15N-labeled azides see: Leseticky, L.; Barth, R.; Nemec, I.; Sticha, M.; Tislerova, I. Czech. J. Phys. 2003, 53, A777.
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-
-
-
106
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36849075654
-
-
See supporting information for the synthesis and characterization of this compound
-
See supporting information for the synthesis and characterization of this compound.
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-
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107
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3543069331
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Starikova, O. V.; Dolgushin, G. V.; Larina, L. I.; Ushakov, P. E.; Komarova, T. N.; Lopyrev, V. A. Russ. J. Org. Chem. 2003, 39, 1467.
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(2003)
Russ. J. Org. Chem
, vol.39
, pp. 1467
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Starikova, O.V.1
Dolgushin, G.V.2
Larina, L.I.3
Ushakov, P.E.4
Komarova, T.N.5
Lopyrev, V.A.6
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108
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0002444477
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Gehrhus, B.; Hitchcock, P. B.; Lappert, M. F. J. Chem. Soc., Dalton Trans. 2000, 3094.
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(2000)
J. Chem. Soc., Dalton Trans
, pp. 3094
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Gehrhus, B.1
Hitchcock, P.B.2
Lappert, M.F.3
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