Citation: CHENG Xue-Li. Density Functional Theory Investigation on the Reaction Mechanisms of Ti (³F) with CH₂Cl₂ and CHCl₃ to CH₂=TiCl₂ and HC÷TiCl₃[J]. Chinese Journal of Structural Chemistry, ;2016, 35(2): 193-198. doi: 10.14102/j.cnki.0254-5861.2011-0862 shu

Density Functional Theory Investigation on the Reaction Mechanisms of Ti (³F) with CH₂Cl₂ and CHCl₃ to CH₂=TiCl₂ and HC÷TiCl₃

CHENG Xue-Li ^,

1.
School of Chemistry and Chemical Engineering, Taishan University, Tai'an, Shandong 271021, China

Corresponding author: CHENG Xue-Li,
Received Date: 23 June 2015
Available Online: 21 August 2015
Fund Project: This work was financially supported by the National Natural Science Foundation of China (11174215) (11174215)the University Science and Technology Project of Shandong Province (No. J13LD05) (ZR2012BL10)

The reaction mechanisms of Ti (³F) + CH₂Cl₂ → CH₂=TiCl₂ and Ti (³F) + CHCl₃ → HC÷TiCl₃ were investigated with Gaussian 03 program package at the B3PW91/6-311++G(d,p) level. The computational results revealed that: 1) Both reaction systems are initiated by Ti (³F) atom attacking the C atom of CH₂Cl₂ and CHCl₃ to activate a C-Cl bond; 2) Both reaction systems were carried out via triplet reaction channels; 3) CH₂=TiCl₂ has singlet and triplet isomers, and the singlet one is more stable; 4) The HOMO of CH₂=TiCl₂(S) illustrates a π-bonding interaction between C and Ti; 5) Only singlet HC÷TiCl₃ was located, and the Mülliken atomic spin densities show that the two single electrons are mostly on the C atom.
- B3PW91,
- reaction mechanism,
- Ti (³F),
- CH₂=TiCl₂,
- HC÷TiCl₃
1. [1]
  (1) Hippler, M. Quantum chemical study and infrared spectroscopy of hydrogen-bonded CHCl₃-NH₃ in the gas phase. J. Chem. Phys. 2007, 127, 084306-10.
2. [2]
  (2) Chen, Y.; Wen, Y.; Zhou, J.; Zhou, Q.; Jan Vymazal, J.; Kuschk, P. Transformation of chloroform in model treatment wetlands: from mass balance to microbial analysis. Environ. Sci. Technol. 2015, 49, 6198-6205.
3. [3]
  (3) Yan, T. H.; Tsai, C. C.; Chien, C. T.; Cho, C. C.; Huang, P. C. Dichloromethane activation. Direct methylenation of ketones and aldehydes with CH₂Cl₂ promoted by Mg/TiCl₄/THF. Org. Lett. 2004, 6, 4961-4963.
4. [4]
  (4) Abou-Chahine, F.; Preston, T. J.; Dunning, G. T.; Orr-Ewing, A. J.; Greetham, G. M.; Clark, I. P.; Towrie, M.; Reid, S. A. Photoisomerization and photoinduced reactions in liquid CCl₄ and CHCl₃. J. Phys. Chem. A 2013, 117, 13388-13398.
5. [5]
  (5) Vila, F. D.; Strubbe, D. A.; Takimoto, Y.; Andrade, X.; Rubio, A.; Louie, S. G.; Rehr, J. J. Basis set effects on the hyperpolarizability of CHCl₃: Gaussian-type orbitals, numerical basis sets and real-space grids. J. Chem. Phys. 2010, 133, 034111-10.
6. [6]
  (6) Lemieux, P. M.; Ryan. J. V.; Bass, C.; Barat, R. Emissions of trace products of incomplete combustion from a pilot-scale incinerator secondary combustion chamber. J. Air Waste Manag. Assoc. 1996, 46, 309-316.
7. [7]
  (7) Preis, S.; Kallas, J. Gas-phase degradation of CCl₄, CHCl₃ and CH₂Cl₂ over metallic Fe. Environ. Chem. Lett. 2004, 2, 9-13.
8. [8]
  (8) Dias, H. V. R.; Browning, R. G.; Polach, S. A.; Diyabalanage, H. V. K.; Lovely, C. J. Activation of alkyl halides via a silver-catalyzed carbene insertion process. J. Am. Chem. Soc. 2003, 125, 9270-9271.
9. [9]
  (9) Csok, Z.; Vechorkin, O.; Harkins, S. B.; Scopelliti, R.; Hu, X. Nickel complexes of a pincer NN₂ ligand: multiple carbon-chloride activation of CH₂Cl₂ and CHCl₃ leads to selective carbon-carbon bond formation. J. Am. Chem. Soc. 2008, 130, 8156-8157.
10. [10]
  (10) Li, G. B.; Liu, J. M.; Yu, Z. Q.; Wang, W.; Su, C. Y. Assembly of a 1D coordination polymer through in situ formation of a new ligand by double C-C coupling on CHCl₃ under solvothermal conditions. Inorg. Chem. 2009, 48, 8659-8661.
11. [11]
  (11) Lin, K. W.; Tsai, C. H.; Hsieh, I. L.; Yan, T. H. New, general, and practical preparation of methyl ketones via the direct coupling of amides with CH₂Cl₂ promoted by TiCl₄/Mg. Org. Lett. 2008, 10, 1927-1930.
12. [12]
  (12) Lyon, J. T.; Andrews, L. An infrared spectroscopic and theoretical study of group 4 transition metal CH₂=MCl₂ and HC÷MCl₃ complexes. Organometallics 2007, 26, 332-339.
13. [13]
  (13) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Oritz, J. V.; Stefanov, B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian, Inc., Wallingford CT 2004, Gaussian 03, Revision C.02.
14. [14]
  (14) Perdew, J. P.; Burke, K.; Wang, Y. Generalized gradient approximation for the exchange-correlation hole of a many-electron system. Phys. Rev. B 1996, 54, 16533-16533.
15. [15]
  (15) Burke, K.; Perdew, J. P.; Wang, Y. Electronic Density Functional Theory: Recent Progress and New Directions, ed. Donson, J. F.; Vignale, G.; Das M. P. Plenum Press, New York 1998.
16. [16]
  (16) Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 1988, 38, 3098-3100.
17. [17]
  (17) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B 1992, 46, 6671-6687.
18. [18]
  (18) Gonzalez, C.; Schlegel, H. B. Reaction path following in mass-weighted internal coordinates. J. Phys. Chem. 1990, 94, 5523-5527.
19. [19]
  (19) Gonzalez, C.; Schlegel, H. B. An improved algorithm for reaction path following. J. Chem. Phys. 1989, 90, 2154-2159.
20. [20]
  (20) Pandey, L. B.; Aikens, C. M. Theoretical investigation of the electrochemical mechanism of water splitting on a titanium oxide cluster model. J. Phys. Chem. A 2012, 116, 526-535.
21. [21]
  (21) Schwarz, A. D.; Nova, A.; Clot, E.; Mountford, P. Titanium tert-butoxyimido compounds. Inorg. Chem. 2011, 50, 12155-12171.
22. [22]
  (22) Flisak, Z. Thermodynamics of titanium and vanadium reduction in non-aqueous environment calculated at various levels of theory. J. Phys. Chem. A 2012, 116, 1464-1468.
23. [23]
  (23) Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 1993, 98, 5648-5652.
1. [1]
  Zhen Liu , Zhi-Yuan Ren , Chen Yang , Xiangyi Shao , Li Chen , Xin Li . Asymmetric alkenylation reaction of benzoxazinones with diarylethylenes catalyzed by B(C₆F₅)₃/chiral phosphoric acid. Chinese Chemical Letters, 2024, 35(5): 108939-. doi: 10.1016/j.cclet.2023.108939
2. [2]
  Xiuzheng Deng , Changhai Liu , Xiaotong Yan , Jingshan Fan , Qian Liang , Zhongyu Li . Carbon dots anchored NiAl-LDH@In₂O₃ hierarchical nanotubes for promoting selective CO₂ photoreduction into CH₄. Chinese Chemical Letters, 2024, 35(6): 108942-. doi: 10.1016/j.cclet.2023.108942
3. [3]
  Zizhuo Liang , Fuming Du , Ning Zhao , Xiangxin Guo . Revealing the reason for the unsuccessful fabrication of Li3Zr2Si2PO12 by solid state reaction. Chinese Journal of Structural Chemistry, 2023, 42(11): 100108-100108. doi: 10.1016/j.cjsc.2023.100108
4. [4]
  Haojie Duan , Hejingying Niu , Lina Gan , Xiaodi Duan , Shuo Shi , Li Li . Reinterpret the heterogeneous reaction of α-Fe₂O₃ and NO₂ with 2D-COS: The role of SDS, UV and SO₂. Chinese Chemical Letters, 2024, 35(6): 109038-. doi: 10.1016/j.cclet.2023.109038
5. [5]
  Min WANG , Dehua XIN , Yaning SHI , Wenyao ZHU , Yuanqun ZHANG , Wei ZHANG . Construction and full-spectrum catalytic performance of multilevel Ag/Bi/nitrogen vacancy g-C₃N₄/Ti₃C₂T_x Schottky junction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1123-1134. doi: 10.11862/CJIC.20230477
6. [6]
  Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei . Efficient Photocatalytic H₂O₂ Production and Cr(VI) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309020-. doi: 10.3866/PKU.WHXB202309020
7. [7]
  Ke-Ai Zhou , Lian Huang , Xing-Ping Fu , Li-Ling Zhang , Yu-Ling Wang , Qing-Yan Liu . Fluorinated metal-organic framework for methane purification from a ternary CH4/C2H6/C3H8 mixture. Chinese Journal of Structural Chemistry, 2023, 42(11): 100172-100172. doi: 10.1016/j.cjsc.2023.100172
8. [8]
  Kaihui Huang , Boning Feng , Xinghua Wen , Lei Hao , Difa Xu , Guijie Liang , Rongchen Shen , Xin Li . Effective photocatalytic hydrogen evolution by Ti3C2-modified CdS synergized with N-doped C-coated Cu2O in S-scheme heterojunctions. Chinese Journal of Structural Chemistry, 2023, 42(12): 100204-100204. doi: 10.1016/j.cjsc.2023.100204
9. [9]
  Yaping Wang , Pengcheng Yuan , Zeyuan Xu , Xiong-Xiong Liu , Shengfa Feng , Mufan Cao , Chen Cao , Xiaoqiang Wang , Long Pan , Zheng-Ming Sun . Ti₃C₂T_x MXene in-situ transformed Li₂TiO₃ interface layer enabling 4.5 V-LiCoO₂/sulfide all-solid-state lithium batteries with superior rate capability and cyclability. Chinese Chemical Letters, 2024, 35(6): 108776-. doi: 10.1016/j.cclet.2023.108776
10. [10]
  Guangchang Yang , Shenglong Yang , Jinlian Yu , Yishun Xie , Chunlei Tan , Feiyan Lai , Qianqian Jin , Hongqiang Wang , Xiaohui Zhang . Regulating local chemical environment in O3-type layered sodium oxides by dual-site Mg²⁺/B³⁺ substitution achieves durable and high-rate cathode. Chinese Chemical Letters, 2024, 35(9): 109722-. doi: 10.1016/j.cclet.2024.109722
11. [11]
  Fengrui Yang , Debing Wang , Xinying Zhang , Jie Zhang , Zhichao Wu , Qiaoying Wang . Synergistic effects of peroxydisulfate on UV/O₃ process for tetracycline degradation: Mechanism and pathways. Chinese Chemical Letters, 2024, 35(10): 109599-. doi: 10.1016/j.cclet.2024.109599
12. [12]
  Juan Guo , Mingyuan Fang , Qingsong Liu , Xiao Ren , Yongqiang Qiao , Mingju Chao , Erjun Liang , Qilong Gao . Zero thermal expansion in Cs₂W₃O₁₀. Chinese Chemical Letters, 2024, 35(7): 108957-. doi: 10.1016/j.cclet.2023.108957
13. [13]
  Rong-Nan Yi , Wei-Min He . Photocatalytic Minisci-type multicomponent reaction for the synthesis of 1-(halo)alkyl-3-heteroaryl bicyclo[1.1.1]pentanes. Chinese Chemical Letters, 2024, 35(10): 110115-. doi: 10.1016/j.cclet.2024.110115
14. [14]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
15. [15]
  Ming ZHENG , Yixiao ZHANG , Jian YANG , Pengfei GUAN , Xiudong LI . Energy storage and photoluminescence properties of Sm³⁺-doped Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ lead-free multifunctional ferroelectric ceramics. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 686-692. doi: 10.11862/CJIC.20230388
16. [16]
  Renshu Huang , Jinli Chen , Xingfa Chen , Tianqi Yu , Huyi Yu , Kaien Li , Bin Li , Shibin Yin . Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100171-100171. doi: 10.1016/j.cjsc.2023.100171
17. [17]
  Maomao Liu , Guizeng Liang , Ningce Zhang , Tao Li , Lipeng Diao , Ping Lu , Xiaoliang Zhao , Daohao Li , Dongjiang Yang . Electron-rich Ni2+ in Ni3S2 boosting electrocatalytic CO2 reduction to formate and syngas. Chinese Journal of Structural Chemistry, 2024, 43(8): 100359-100359. doi: 10.1016/j.cjsc.2024.100359
18. [18]
  Ya-Nan Yang , Zi-Sheng Li , Sourav Mondal , Lei Qiao , Cui-Cui Wang , Wen-Juan Tian , Zhong-Ming Sun , John E. McGrady . Metal-metal bonds in Zintl clusters: Synthesis, structure and bonding in [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–. Chinese Chemical Letters, 2024, 35(8): 109048-. doi: 10.1016/j.cclet.2023.109048
19. [19]
  Ping Lu , Baoyin Du , Ke Liu , Ze Luo , Abiduweili Sikandaier , Lipeng Diao , Jin Sun , Luhua Jiang , Yukun Zhu . Heterostructured In2O3/In2S3 hollow fibers enable efficient visible-light driven photocatalytic hydrogen production and 5-hydroxymethylfurfural oxidation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100361-100361. doi: 10.1016/j.cjsc.2024.100361
20. [20]
  Yan Cheng , Hua-Peng Ruan , Yan Peng , Longhe Li , Zhenqiang Xie , Lang Liu , Shiyong Zhang , Hengyun Ye , Zhao-Bo Hu . Magnetic, dielectric and luminescence synergetic switchable effects in molecular material [Et₃NCH₂Cl]₂[MnBr₄]. Chinese Chemical Letters, 2024, 35(4): 108554-. doi: 10.1016/j.cclet.2023.108554

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(697)
HTML views(4)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Density Functional Theory Investigation on the Reaction Mechanisms of Ti (3F) with CH2Cl2 and CHCl3 to CH2=TiCl2 and HC÷TiCl3

Metrics

通讯作者: 陈斌, bchen63@163.com

Density Functional Theory Investigation on the Reaction Mechanisms of Ti (³F) with CH₂Cl₂ and CHCl₃ to CH₂=TiCl₂ and HC÷TiCl₃