Ion-Molecule Reaction of Ti+ Ion with Trifluoroacetone in the Gas Phase
International Journal of Computational and Theoretical Chemistry
Volume 7, Issue 1, June 2019, Pages: 56-64
Received: Feb. 2, 2019; Accepted: Mar. 19, 2019; Published: Apr. 29, 2019
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Dababrata Paul, Department of Chemistry, Bangabandhu Sheikh Mujibur Rahman Science and Technology University, Gopalganj, Bangladesh
Kiryong Hong, Center for Gas Analysis, Division of Chemical and Medical Metrology, Korea Research Institute of Standards and Science, Daejeon, Republic of Korea
Md. Mostafizur Rahman, Department of Chemistry, Shahjalal University of Science and Technology, Sylhet, Bangladesh
Shishir Kanti Pramanik, Department of Chemistry, Shahjalal University of Science and Technology, Sylhet, Bangladesh
Tae Kyu Kim, Department of Chemistry and Chemistry Institute of Functional Materials, Pusan National University, Busan, Republic of Korea
Kwang-Woo Jung, Department of Chemistry and Institute of Nanoscience & Technology, Wonkwang University, Iksan, Chonbuk, Republic of Korea
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Gas-phase ion-molecule reactions of Ti+ with 1,1,1-trifluoroacetone were studied by laser ablation/molecular-beam method and density function theory calculations. In the reaction of the Ti+ ions with acetone, Ti+ ion insertion into the C=O bond is the preferred decomposition pathway and produce TiO+ predominantly. Substitution of CH3 in acetone molecule with electronegative CF3 group greatly alters the reaction pathway, which is confirmed from TiF2+ and TiO+ observations by mass spectrometry. This is interpreted as the dominant reaction channels via Ti+ insertions into C–F and C=O bonds of trifluoroacetone molecule. In addition, geometries and energies of the intermediates and transition states involved in two pathways are located by DFT calculations. On the basis of these results, two pathways are considered as competitive and the most favorable pathway proceeds via Ti+ induced C–F bond activation processes.
Ion-molecule Reaction, Titanium, 1,1,1-Trifluoroacetone, Mass Spectrometry
To cite this article
Dababrata Paul, Kiryong Hong, Md. Mostafizur Rahman, Shishir Kanti Pramanik, Tae Kyu Kim, Kwang-Woo Jung, Ion-Molecule Reaction of Ti+ Ion with Trifluoroacetone in the Gas Phase, International Journal of Computational and Theoretical Chemistry. Vol. 7, No. 1, 2019, pp. 56-64. doi: 10.11648/j.ijctc.20190701.18
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R. C. Burnier, G. D. Byrd, and B. S. Freiser, “Gas-phase reactions of iron (1+) with ketones and ethers,’’ J. Am. Chem. Soc., vol. 103, pp. 4360-4367, July 1981.
L. F. Halle, W. E. Crowe, P. B. Armentrout, and J. L. Beauchamp, “Reactions of atomic cobalt ions with aldehydes and ketones. Observation of decarbonylation processes leading to formation of metal alkyls and metallacycles in the gas phase,” Organometallics, vol. 3, pp. 1694-1706, November 1984.
S. S. Yi, E. L. Reichert, and J. C. Weisshaar, “Bimolecular reaction dynamics of Co+ (3F4) + acetone reaction in real time,” Int. J. Mass Spectrom., vol. 185, pp. 837-846, April 1999.
J. B. Schilling, and J. L. Beauchamp, “Hydrocarbon activation by gas-phase lanthanide cations: interaction of praseodymium (Pr+), europium (Eu+), and gadolinium (Gd+) with small alkanes, cycloalkanes, and alkenes,” J. Am. Chem. Soc., vol. 110, pp. 15-24, January 1988.
M. A. Tolbert, and J. L. Beauchamp, “Activation of carbon-hydrogen and carbon-carbon bonds by transition-metal ions in the gas phase. Exhibition of unique reactivity by scandium ions,” J. Am. Chem. Soc., vol. 106, pp. 8117-8122, Decmber 1984.
U. Mazurek, K. Koszinowski, and H. Schwarz, “C−F bond activation in fluorinated carbonyl compounds by chromium monocations in the gas phase,” Organometallics, vol. 22, pp. 218-222, December 2002.
U. Mazurek, D. Schroder, and H. Schwarz, “Hydrolytic activation of C-F bonds in the gas phase by intrinsically unreactive chromium cations,” Angew. Chem. Int. Ed., vol. 41, pp. 3085-3095, August 2002.
X. F. Chen, W. Y. Guo, L. M. Zhao, and Q. T. Fu, “Theoretical survey of the potential energy surface of Ni+ + acetone reaction,” Chem. Phys. Lett., vol. 432, pp. 27-32, December 2006.
J. Kim, T. K. Kim, and H. Ihee, “Theoretical study on the reaction of Ti+ with acetone and the role of intersystem crossing,” J. Phys. Chem. A, vol. 113, pp. 11382-11389, September 2009.
Y. M. Koo, H. J. An, S. K. Yoo, and K. W. Jung, “Intracluster ion-molecule reactions of Ti+ with ethanol and t-butanol clusters,” Int. J. Mass Spectrom., vol. 226, pp. 305-316, April 2003.
Y. M. Koo, J. H. Kim, Y. K. Choi, H. Lee, and K. W. Jung, “Intracluster ion-molecule reactions of Ti+ with methanol clusters,” J. Phys. Chem. A, vol. 106, pp. 2465-2472, February 2002.
Y. M. Koo, T. K. Kim, D. W. Jung, and K. W. Jung, “Intracluster ion-molecule reactions of Ti+ with C2H5OH and CF3CH2OH clusters:   Influence of fluorine substituents on chemical reactivity,” J. Phys. Chem. A, vol. 110, pp. 13724-13730, December 2006.
A. D. Becke, “A new mixing of Hartree–Fock and local density‐functional theories” J. Chem. Phys., vol. 98, pp. 1372-1377, January 1993.
C. T. Lee, W. T. Yang, and R. G. Parr, “Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density,” Phys. Rev. B, vol. 37, pp. 785-789, January 1988.
C. Gonzalez, and H. B. Schlegel, “An improved algorithm for reaction path following,” J. Chem. Phys., “vol. 90, pp. 2154-2161, February 1989.
C. Gonzalez, and H. B. Schlegel, “Reaction path following in mass-weighted internal coordinates,” J. Phys. Chem., vol. 94, pp. 5523-5527, July 1990.
A. E. Reed, L. A. Curtiss, and F. Weinhold, “Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint,” Chem. Rev., vol. 88, pp. 899-926, September 1988.
A. E. Reed, R. B. Weinstock, and F. Weinhold, “Natural population analysis,” J. Chem. Phys., vol. 83, pp. 735-746, July 1985.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. J. A. Montgomery, 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, 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, and J. A. Pople, Gaussian 03, Revision C. 02, in, Gaussian, Inc., Wallingford CT, 2004.
Y. M. Koo, K. Hong, T. K. Kim, and K. W. Jung, “Intramolecular ion-molecule reactions within Ti+ (CH3COCH3)n heteroclusters: Oxidation pathway via C=O bond activation,” Bull. Korean Chem. Soc., vol. 31, pp. 953-958, March 2010.
W. Y. Guo, H. C. Liu, and S. H. Yang, “Photo-induced intra-complex reactions in Mg+-2, 2, 2-trifluoroethanol” J. Chem. Phys., vol. 116, pp. 9690-9696, June 2002.
M. Lombarski, and J. Allison, “The gas-phase chemistry of metal and metal-containing ions with multifunctional organic molecules-investigating the utility of such ions as chemical-ionization reagents,” Int. J. Mass Spectrom. Ion Phys., vol. 49, pp. 281-299, April 1983.
D. Caraiman, G. K. Koyanagi, and D. K. Bohme, “Gas-Phase reactions of transition-metal ions with hexafluorobenzene:   Room-temperature kinetics and periodicities in reactivity,” J. Phys. Chem. A, vol. 108, pp. 978-986, January 2004.
H. C. Liu, C. S. Wang, W. Guo, Y. D. Wu, and S. H. Yang, “Formation and decomposition of distonic o-, m-, and p-benzyne radical cations from photolysis of Mg+ (o-, m-, p-C6H4F2),” J. Am. Chem. Soc., vol. 124, pp. 3794-3798, March 2002.
L. S. Sunderlin, and P. B. Armentrout, “Methane activation by titanium (1+): electronic and translational energy dependence,” J. Phys. Chem., vol. 92, pp. 1209-1219, March 1988.
L. M. Zhao, R. R. Zhang, W. Y. Guo, and X. Q. Lu, “The oxidation pathways of Ti+ by acetaldehyde in the gas phase: A density functional theory investigation,” Chem. Phys. Lett., vol. 431, pp. 56-61, November 2006.
X. Wang, Y. Wang, S. Li, Y. Zhang, and P. Ma, “Theoretical study on the reaction mechanism of Ti with CH3CN in the gas phase,” J. Phys. Chem. A, vol. 120, pp. 5457-5463, July 2016.
P. Sharma, I. Attah, P. Momoh, and M. S. El-Shall, “Metal acetylene cluster ions M+ (C2H2)n as model reactors for studying reactivity of laser-generated transition metal cations,” Int. J. Mass Spectrom., vol. 300, pp. 81-90, March 2011.
H. Wasada, Y. Wasada-Tsutsui, T. Hashimoto, and S. Funahashi, “Theoretical study of acetonitrile‐exchange reactions on hexasolvated divalent cations in the first transition series elements,” Int. J. Quant. Chem., vol. 109, pp. 2208-2226, March 2009.
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