8.3 C−H Bond Activation
137
From the DFT calculations, both 1-butene and 2-butene are likely formed on the
basis of a similar reaction mechanism [59].
The cluster reactivity towards hydrocarbons can be classified to a few aspects,
such as: (i) direct association, (ii) C−H bond activation, (iii) C−C bond or C=C
cracking, and (iv) O-atom transfer. These reactivities are coincident with calculated
reaction coordinates via first-principles theory. By combining photoelectron spectral
studies, comparable electronic transitions and orbital symmetry were found for WC
versus Pt; Ni versus TiO, Pd versus ZrO, revealing commonality in their electronic
spectra. On the basis of these experimental findings, it was proposed that ZrO can
be viewed as the superatomic form of Pd, or at least they have similar electronic
structures within 2.33 eV of the highest occupied molecular orbital (HOMO) of the
anion. Similarly, TiO is mimic of Ni; as well as Pt versus WC.
References
1. A.W. Castleman Jr., S. Wei, Annu. Rev. Phys. Chem. 45, 685–719 (1994)
2. K.A. Zemski, D.R. Justes, A.W. Castleman Jr., J. Phys. Chem. B 106, 6136–6148 (2002)
3. D. Paul, K. Hong, T.K. Kim, J.-S. Oh, K.-W. Jung, Int. J. Mass Spectrom. 315, 15–21 (2012)
4. M.T. Bowers, Gas Phase Ion Chemistry (Academic Press, New York, 1979)
5. J.F. Garvey, W.R. Peifer, M.T. Coolbaugh, Acc. Chem. Res. 24, 48–54 (1991)
6. R.C. Bell, K.A. Zemski, K.P. Kerns, H.T. Deng, A.W. Castleman Jr., J. Phys. Chem. A 102,
1733–1742 (1998)
7. R.C. Bell, K.A. Zemski, A.W. Castleman Jr., J. Phys. Chem. A 102, 8293–8299 (1998)
8. R.C. Bell, A.W. Castleman Jr., D.L. Thorn, Inorg. Chem. 38, 5709–5715 (1999)
9. R.C. Bell, K.A. Zemski, A.W. Castleman Jr., J. Phys. Chem. A 103, 1585–1591 (1999)
10. R.C. Bell, K.A. Zemski, A.W. Castleman Jr., J. Phys. Chem. A 103, 2992–2998 (1999)
11. K.A. Zemski, R.C. Bell, A.W. Castleman Jr., J. Phys. Chem. A 104, 5732–5741 (2000)
12. R.C. Bell, K.A. Zemski, D.R. Justes, A.W. Castleman Jr., J. Chem. Phys. 114, 798–811 (2001)
13. K.A. Zemski, R.C. Bell, D.R. Justes, A.W. Castleman, Jr., A brief summary of reactions of
group V transition metal oxide cluster ions with butane (2001)
14. K.A. Zemski, D.R. Justes, R.C. Bell, A.W. Castleman Jr., J. Phys. Chem. A 105, 4410–4417
(2001)
15. K.A. Zemski, D.R. Justes, A.W. Castleman Jr., J. Phys. Chem. A 105, 10237–10245 (2001)
16. R.C. Bell, A.W. Castleman Jr., J. Phys. Chem. A 106, 9893–9899 (2002)
17. D.R. Justes, A.W. Castleman Jr., R. Mitric, V. Bonacic-Koutecky, Europ. Phys. J. D 24,
331–334 (2003)
18. D.R. Justes, R. Mitric, N.A. Moore, V. Bonacic-Koutecky, A.W. Castleman Jr., J. Am. Chem.
Soc. 125, 6289–6299 (2003)
19. J.R. Stairs, S.J. Peppernick, K.M. Davis, A.W. Castleman Jr., Isr. J. Chem. 44, 223–228 (2004)
20. N.A. Moore, R. Mitric, D.R. Justes, V. Bonacic-Koutecky, A.W. Castleman Jr., J. Phys. Chem.
B 110, 3015–3022 (2006)
21. C. Berg, T. Schindler, G. Niednerschatteburg, V.E. Bondybey, J. Chem. Phys. 102, 4870–4884
(1995)
22. C. Berg, M. Beyer, U. Achatz, S. Joos, G. Niedner-Schatteburg, V.E. Bondybey, J. Chem.
Phys. 108, 5398–5403 (1998)
23. Y. Xie, S.G. He, F. Dong, E.R. Bernstein, J. Chem. Phys. 128, 044306 (2008)
24. K.A. Zemski, R.C. Bell, A.W. Castleman Jr., Int. J. Mass Spectrom. 184, 119–128 (1999)
25. A. Božovi´ c, S. Feil, G.K. Koyanagi, A.A. Viggiano, X. Zhang, M. Schlangen, H. Schwarz,
D.K. Bohme, Chem. Eur. J. 16, 11605–11610 (2010)
137
From the DFT calculations, both 1-butene and 2-butene are likely formed on the
basis of a similar reaction mechanism [59].
The cluster reactivity towards hydrocarbons can be classified to a few aspects,
such as: (i) direct association, (ii) C−H bond activation, (iii) C−C bond or C=C
cracking, and (iv) O-atom transfer. These reactivities are coincident with calculated
reaction coordinates via first-principles theory. By combining photoelectron spectral
studies, comparable electronic transitions and orbital symmetry were found for WC
versus Pt; Ni versus TiO, Pd versus ZrO, revealing commonality in their electronic
spectra. On the basis of these experimental findings, it was proposed that ZrO can
be viewed as the superatomic form of Pd, or at least they have similar electronic
structures within 2.33 eV of the highest occupied molecular orbital (HOMO) of the
anion. Similarly, TiO is mimic of Ni; as well as Pt versus WC.
References
1. A.W. Castleman Jr., S. Wei, Annu. Rev. Phys. Chem. 45, 685–719 (1994)
2. K.A. Zemski, D.R. Justes, A.W. Castleman Jr., J. Phys. Chem. B 106, 6136–6148 (2002)
3. D. Paul, K. Hong, T.K. Kim, J.-S. Oh, K.-W. Jung, Int. J. Mass Spectrom. 315, 15–21 (2012)
4. M.T. Bowers, Gas Phase Ion Chemistry (Academic Press, New York, 1979)
5. J.F. Garvey, W.R. Peifer, M.T. Coolbaugh, Acc. Chem. Res. 24, 48–54 (1991)
6. R.C. Bell, K.A. Zemski, K.P. Kerns, H.T. Deng, A.W. Castleman Jr., J. Phys. Chem. A 102,
1733–1742 (1998)
7. R.C. Bell, K.A. Zemski, A.W. Castleman Jr., J. Phys. Chem. A 102, 8293–8299 (1998)
8. R.C. Bell, A.W. Castleman Jr., D.L. Thorn, Inorg. Chem. 38, 5709–5715 (1999)
9. R.C. Bell, K.A. Zemski, A.W. Castleman Jr., J. Phys. Chem. A 103, 1585–1591 (1999)
10. R.C. Bell, K.A. Zemski, A.W. Castleman Jr., J. Phys. Chem. A 103, 2992–2998 (1999)
11. K.A. Zemski, R.C. Bell, A.W. Castleman Jr., J. Phys. Chem. A 104, 5732–5741 (2000)
12. R.C. Bell, K.A. Zemski, D.R. Justes, A.W. Castleman Jr., J. Chem. Phys. 114, 798–811 (2001)
13. K.A. Zemski, R.C. Bell, D.R. Justes, A.W. Castleman, Jr., A brief summary of reactions of
group V transition metal oxide cluster ions with butane (2001)
14. K.A. Zemski, D.R. Justes, R.C. Bell, A.W. Castleman Jr., J. Phys. Chem. A 105, 4410–4417
(2001)
15. K.A. Zemski, D.R. Justes, A.W. Castleman Jr., J. Phys. Chem. A 105, 10237–10245 (2001)
16. R.C. Bell, A.W. Castleman Jr., J. Phys. Chem. A 106, 9893–9899 (2002)
17. D.R. Justes, A.W. Castleman Jr., R. Mitric, V. Bonacic-Koutecky, Europ. Phys. J. D 24,
331–334 (2003)
18. D.R. Justes, R. Mitric, N.A. Moore, V. Bonacic-Koutecky, A.W. Castleman Jr., J. Am. Chem.
Soc. 125, 6289–6299 (2003)
19. J.R. Stairs, S.J. Peppernick, K.M. Davis, A.W. Castleman Jr., Isr. J. Chem. 44, 223–228 (2004)
20. N.A. Moore, R. Mitric, D.R. Justes, V. Bonacic-Koutecky, A.W. Castleman Jr., J. Phys. Chem.
B 110, 3015–3022 (2006)
21. C. Berg, T. Schindler, G. Niednerschatteburg, V.E. Bondybey, J. Chem. Phys. 102, 4870–4884
(1995)
22. C. Berg, M. Beyer, U. Achatz, S. Joos, G. Niedner-Schatteburg, V.E. Bondybey, J. Chem.
Phys. 108, 5398–5403 (1998)
23. Y. Xie, S.G. He, F. Dong, E.R. Bernstein, J. Chem. Phys. 128, 044306 (2008)
24. K.A. Zemski, R.C. Bell, A.W. Castleman Jr., Int. J. Mass Spectrom. 184, 119–128 (1999)
25. A. Božovi´ c, S. Feil, G.K. Koyanagi, A.A. Viggiano, X. Zhang, M. Schlangen, H. Schwarz,
D.K. Bohme, Chem. Eur. J. 16, 11605–11610 (2010)