278
L. Bini et al. / Catalysis Today 155 (2010) 271–278
[2] C.A. Tolman, Chem. Rev. 77 (1977) 313.
4. Conclusions
[3] A. Chaumonnot, F. Lamy, S. Sabo-Etienne, B. Donnadieu, B. Chaudret, J.C. Barthelat,
J.C. Galland, Organometallics 23 (2004) 3363.
The isomerization of 2M3BN was performed in dioxane at 60 8C
for 4 h using a triptycene-based diphosphine ligand in combina-
tion with Ni(cod)2. A final conversion of 87% was determined by
GC-analysis. IR spectra were recorded every 10 min using an ATR
probe connected with a flexible light guide to a FTIR instrument.
Different regions in the spectra were analyzed. The peak in the –
CN stretch region at 2243 cmÀ1 gradually decreased and a second
peak at 2248 cmÀ1 arose, while the 2M3BN is converted into 3PN.
Also the CH deformation and the (C55)CH stretch regions showed
transformations in time. Several spectral regions have been
transformed to their second derivative. The dynamics in the
spectra were calculated and normalized to the final conversion
determined by GC. Similar kinetic profiles were obtained from the
dynamics of different bands. Furthermore, DFT calculations have
been performed to obtain calculated IR spectra of 2M3BN, trans-
and cis-3PN, in order to assign the corresponding bands in the
spectra of the mixture. An average kinetic profile was obtained
from the dynamics of four different peaks in the spectra applying a
‘‘quasi-multivariate’’ analysis (QMV), taking into consideration the
correlated formation of 3PN and consumption of 2M3BN.
[4] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination
Compounds, 3rd ed., Wiley, 1978.
[5] J.I. van der Vlugt, A.C. Hewat, S. Neto, R. Sablong, A.M. Mills, M. Lutz, A.L. Spek, C.
Mu¨ ller, D. Vogt, Adv. Synth. Catal. 346 (2004) 993.
[6] A. Acosta-Ramirez, M. Mun˜oz-Hernandez, W.D. Jones, J.J. Garcia, J. Organomet.
Chem. 691 (2006) 3895.
[7] A. Acosta-Ramirez, M. Mun˜oz-Hernandez, W.D. Jones, J.J. Garcia, Organometallics
26 (2007) 5766.
[8] W. Goertz, W. Keim, D. Vogt, U. Englert, M.D.K. Boele, L.A. van de Veen, P.C.J.
Kamer, P.W.N.M. van Leeuwen, J. Chem. Soc. Dalton Trans. (1998) 2981.
[9] T. Foo, J.M. Garner, Tam, WO 99/06357 (1999), Chem. Abstr., 130 (1999) 169815.
[10] M. Bartsch, R. Baumann, D.P. Kunsmann-Keitel, G. Haderlein, T. Jungkamp, M.
Altmayer, W. Siegel, F. Molnar, DE 10150286 (2003), Chem. Abstr., 138 (2005)
304408.
[11] C.P. Lenges, WO 03/076394 (2003), Chem. Abstr., 139 (2006) 262467.
[12] N.M. Brunkan, D.M. Brestensky, W.D. Jones, J. Am. Chem. Soc. 126 (2004) 3627.
[13] J. Wilting, C. Mu¨ ller, A.C. Hewat, D.D. Ellis, D.M. Tooke, A.L. Spek, D. Vogt,
Organometallics 24 (2005) 13.
[14] A. Acosta-Ramirez, A. Flores-Gaspar, M. Mun˜oz-Hernandez, A. Arevalo, W.D.
Jones, J.J. Garcia, Organometallics 26 (2007) 1712.
[15] B.D. Swartz, N.M. Reinartz, W.W. Brennessel, J.J. Garcia, W.D. Jones, J. Am. Chem.
Soc. 130 (2008) 8548.
[16] G. Maki, J. Chem. Phys. 15 (1958) 5.
[17] C.A. Tolman, W.C. Seidel, J.D. Druliner, P.J. Domaille, Organometallics 3 (1984) 33.
[18] J.D. Druliner, Organometallics 3 (1984) 205.
[19] N.J. Harrick, Internal Reflection Spectroscopy, Wiley, New York, 1967.
[20] P.R. Griffiths, J.A. de Haseth, Fourier Transform Infrared Spectroscopy, Wiley, New
York, 1986.
A
chemometric analysis of the CH deformation region
generated a profile similar to the one obtained via QMV. The
latter method was, therefore, validated as a more accessible
approach to make use of the correlation between different band
dynamics of the significant spectral regions.
[21] B.M. Weckhuysen, Chem. Commun. (2002) 97.
[22] M.O. Guerrero-Perez, M.A. Banarez, Chem. Commun. (2002) 1292.
[23] L. Bini, C. Mu¨ller, J. Wilting, L. von Chrzanowski, A.L. Spek, D. Vogt, J. Am. Chem.
Soc. 128 (2006) 11374.
[24] R.A. Schunn, Inorg. Synth. 15 (1974) 5.
For the first time IR spectroscopy was applied to determine the
kinetics of the 2M3BN isomerization reaction. Improvements in
the FTIR setup would allow in the future the application of such
spectroscopic method also to the study of the hydrocyanation
reaction.
[25] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J.
Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H.
Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B.
Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev,
A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A.
Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C.
Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V.
Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A.
Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham,
C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen,
M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Revision B 05, Gaussian, Inc.,
Pittsburgh, PA, 2003.
Acknowledgements
This work has been financially supported by the National
Research School Combination on Catalysis (NRSCC) and by Evonik
Oxeno. C.M. thanks The Netherlands Organization for Scientific
Research (NWO-CW) for financial support. The authors gratefully
acknowledge Peter Tummers and Ton Staring for technical
assistance.
[26] E. Kitson, N.E. Griffith, Anal. Chem. 24 (1952) 334.
[27] M.R. Whitbeck, Appl. Spectrosc. 35 (1981) 93.
[28] H. Susi, D.M. Byler, Biochem. Biophys. Res. Commun. 115 (1983) 391.
[29] N. Sheppard, Trans. Faraday Soc. 51 (1955) 1465.
[30] N. Sheppard, D.M. Simpson, Quart. Rev. Chem. Soc. 7 (1953) 19.
[31] L.J. Bellamy, R.L. Williams, J. Chem. Soc. Lond. (1956) 2753.
[32] J.J. Fox, A.E. Martin, Proc. Roy. Soc. Ser. A 167 (1938) 257.
[33] F.E. Malherbe, H.J. Berustein, J. Am. Chem. Soc. 17 (1952) 4408.
[34] H.L. McMurry, Thornton, Anal. Chem. 24 (1952) 318.
Appendix A. Supplementary data
[35] E.B. Wilson Jr., J.C. Decius, P.C. Cross, Molecular Vibrations: The Theory of Infrared
and Raman Vibrational Spectra, Dover, New York, 1980.
[36] D.C. Young, Computational Chemistry: A Practical Guide for Applying Techniques
to Real-World Problems, Wiley, New York, 2001.
Supplementary data associated with this article can be found, in
[37] R.J. Meier, Vib. Spectrosc. 43 (2007) 26.
References
[38] H. Martens, T. Naes, Multivariate Calibration, Wiley, New York, 1989.
[39] P.H.G. Tummers, E.J.E. Houben, J.F.G.A. Jansen, D. Wienke, Vib. Spectrosc. 43
(2007) 116.
[1] K. Huthmacher, S. Krill, in: B. Cornils, W.A. Hermann (Eds.), 2nd ed., Applied
Homogeneous Catalysis with Organometallic Compounds, vol. 1, Wiley-VCH,
Weinheim, 2002, p. 465.
[40] K.L.A. Chan, S.G. Kazarin, Appl. Spectrosc. 61 (2007) 48.