Paper
Dalton Transactions
2
3 D. Intrieri, P. Zardi, A. Caselli and E. Gallo, Chem. 51 C. Piangiolino, E. Gallo, A. Caselli, S. Fantauzzi, F. Ragaini
Commun., 2014, 50, 11440–11453.
and S. Cenini, Eur. J. Org. Chem., 2007, 743.
52 N. E. Travia, Z. Xu, J. M. Keith, E. A. Ison, P. E. Fanwick,
M. B. Hall and M. M. Abu-Omar, Inorg. Chem., 2011, 50,
10505–10514.
2
2
2
4 T. Uchida and T. Katsuki, Chem. Rec., 2014, 14, 117–129.
5 T. G. Driver, Org. Biomol. Chem., 2010, 8, 3831–3846.
6 S. A. Cramer and D. M. Jenkins, J. Am. Chem. Soc., 2011,
1
33, 19342–19345.
53 G. Manca, E. Gallo, D. Intrieri and C. Mealli, ACS Catal.,
2014, 4, 823–832.
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
7 S. Cenini, F. Ragaini, E. Gallo and A. Caselli, Curr. Org.
Chem., 2011, 15, 1578–1592.
54 E. Gallo, A. Caselli, F. Ragaini, S. Fantauzzi, N. Masciocchi,
A. Sironi and S. Cenini, Inorg. Chem., 2005, 44, 2039–2049.
55 S. Fantauzzi, E. Gallo, A. Caselli, F. Ragaini, N. Casati,
P. Macchi and S. Cenini, Chem. Commun., 2009, 3952–3954.
56 D. Intrieri, A. Caselli, F. Ragaini, P. Macchi, N. Casati and
E. Gallo, Eur. J. Inorg. Chem., 2012, 569–580.
57 D. Intrieri, A. Caselli, F. Ragaini, S. Cenini and E. Gallo,
J. Porphyrins Phthalocyanines, 2010, 14, 732–740.
58 S. K.-Y. Leung, W.-M. Tsui, J.-S. Huang, C.-M. Che,
J.-L. Liang and N. Zhu, J. Am. Chem. Soc., 2005, 127, 16629–
16640.
8 S. Cenini, E. Gallo, A. Caselli, F. Ragaini, S. Fantauzzi and
C. Piangiolino, Coord. Chem. Rev., 2006, 250, 1234–1253.
9 J. E. Jones, J. V. Ruppel, G.-Y. Gao, T. M. Moore and
X. P. Zhang, J. Org. Chem., 2008, 73, 7260–7265.
0 G.-Y. Gao, J. E. Jones, R. Vyas, J. D. Harden and
X. P. Zhang, J. Org. Chem., 2006, 71, 6655–6658.
1 S. Fantauzzi, E. Gallo, A. Caselli, C. Piangiolino, F. Ragaini
and S. Cenini, Eur. J. Org. Chem., 2007, 6053–6059.
2 A. Caselli, E. Gallo, S. Fantauzzi, S. Morlacchi, F. Ragaini
and S. Cenini, Eur. J. Inorg. Chem., 2008, 3009–3019.
3 S. Cenini, S. Tollari, A. Penoni and C. Cereda, J. Mol. Catal. 59 For the sake of simplicity, the computed allylic amination
A: Chem., 1999, 137, 135–146.
4 Y. Liu and C.-M. Che, Chem. – Eur. J., 2010, 16, 10494–
reaction was illustrated for CH N , although 3,5-bis(tri-
3
3
3
fluoromethyl)phenyl azide (Ar′N ) was experimentally
1
0501.
employed. Such a reactant, also computationally evaluated,
corresponded to a key barrier about 25% lower, but its
energy profile was quite consistent in view of the function-
5 T. W.-S. Chow, G.-Q. Chen, Y. Liu, C.-Y. Zhou and
C.-M. Che, Pure Appl. Chem., 2012, 84, 1685–1704.
6 Y. Fukunaga, T. Uchida, Y. Ito, K. Matsumoto and
T. Katsuki, Org. Lett., 2012, 14, 4658–4661.
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ality of the same azide. On the other hand, Ar′N has a
milder behaviour over the metal centre, since it has more
difficulty in being transformed into diazene Ar′NvNAr′.
This point emerges from comparing the energies for the
reaction 2N R → 2N + RNvNR, which are as different as
7 C. Kim, T. Uchida and T. Katsuki, Chem. Commun., 2012,
4
8, 7188–7190.
8 H. Kawabata, K. Omura, T. Uchida and T. Katsuki, Chem. –
Asian J., 2007, 2, 248–256.
9 L.-M. Jin, X. Xu, H. Lu, X. Cui, L. Wojtas and X. P. Zhang,
Angew. Chem., Int. Ed., 2013, 52, 5309–5313.
0 J. V. Ruppel, J. E. Jones, C. A. Huff, R. M. Kamble, Y. Chen
and X. P. Zhang, Org. Lett., 2008, 10, 1995–1998.
3
2
−105.2 and −71.4 kcal mol− for R = CH
1
and R = Ar′,
3
respectively. For all these reasons, the present study of the
aziridination mechanism generally refers to Ar′N3 as the
reactant of choice.
60 J. T. Groves, J. Chem. Educ., 1985, 62, 928.
1 M. J. Zdilla and M. M. Abu-Omar, J. Am. Chem. Soc., 2006, 61 D. Balcells, C. Raynaud, R. H. Crabtree and O. Eisenstein,
28, 16971–16979. Chem. Commun., 2009, 1772–1774.
2 M. M. Montero-Campillo and M. N. D. S. Cordeiro, 62 J. N. Harvey, R. Poli and K. M. Smith, Coord. Chem. Rev.,
Int. J. Quantum Chem., 2013, 113, 2002–2011. 2003, 238–239, 347–361.
3 A. Sze-Man, J. S. Huang, W. Y. Yu, W. H. Fung and 63 J. N. Harvey and M. Aschi, Faraday Discuss., 2003, 124, 129–
C. M. Che, J. Am. Chem. Soc., 1999, 121, 9120. 143.
4 K. H. Hopmann and A. Ghosh, ACS Catal., 2011, 1, 597– 64 M. Tanno, S. Sueyoshi and S. Kamiya, Chem. Pharm. Bull.,
00. 1982, 30, 3125–3132.
5 A. I. O. Suarez, H. Jiang, X. P. Zhang and B. de Bruin, 65 S. Wiese, M. J. B. Aguila, E. Kogut and T. H. Warren,
Dalton Trans., 2011, 40, 5697–5705. Organometallics, 2013, 32, 2300–2308.
6 S. Cenini, S. Tollari, A. Penoni and C. Cereda, J. Mol. Catal. 66 A. D. Adler, F. R. Longo, J. D. Finarelli, J. Goldmacher,
A: Chem., 1999, 137, 135–146. J. Assour and L. Korsakoff, J. Org. Chem., 1967, 32, 476.
7 C. Piangiolino, E. Gallo, A. Caselli, S. Fantauzzi, F. Ragaini 67 D. P. Rillema, J. K. Nagle, L. F. Barringer and T. J. Meyer,
and S. Cenini, Eur. J. Org. Chem., 2007, 743–750. J. Am. Chem. Soc., 1981, 103, 56–62.
8 S. Fantauzzi, E. Gallo, A. Caselli, F. Ragaini, P. Macchi, 68 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
1
6
N. Casati and S. Cenini, Organometallics, 2005, 24, 4710–
713.
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone,
B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng,
J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda,
J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
H. Nakai, T. Vreven, J. A. Montgomery Jr., J. E. Peralta,
F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers,
4
4
9 A. Caselli, E. Gallo, F. Ragaini, F. Ricatto, G. Abbiati and
S. Cenini, Inorg. Chim. Acta, 2006, 359, 2924–2932.
0 E. Gallo, M. G. Buonomenna, L. Vigano, F. Ragaini,
A. Caselli, S. Fantauzzi, S. Cenini and E. Drioli, J. Mol.
Catal. A: Chem., 2008, 282, 85–91.
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