Citation: Xu Dongdong, Shan Chunhui, Bai Ruopeng, Lan Yu. Mechanism of Alkaline Earth Metal Catalyzed Hydroboration of Carbodiimides: A Theoretical Study[J]. Chinese Journal of Organic Chemistry, ;2017, 37(5): 1231-1236. doi: 10.6023/cjoc201701033 shu

Mechanism of Alkaline Earth Metal Catalyzed Hydroboration of Carbodiimides: A Theoretical Study

Xu Dongdong ^† ,
Shan Chunhui ^† ,
Bai Ruopeng ^*,, ,
Lan Yu ^*,,

School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030

Corresponding author: Bai Ruopeng, ruopeng@cqu.edu.cn Lan Yu, lanyu@cqu.edu.cn
Received Date: 16 January 2017
Revised Date: 24 February 2017

Fund Project: by the National Natural Science Foundation of China 21372266

Figures(4)

Density functional theory (DFT) calculations are employed to study the mechanism of alkaline earth metal catalyzed hydroboration of carbodiimides. Our theoretical study revealed that the active catalytic species is a hydridemagnesium complex when magnesium is used as catalyst. The catalytic cycle starts with a C=N bond insertion into Mg-H bond followed by a B-N bond formation. A hydride transfer from boron to magnesium regenerates the active catalytic species and yields the hydroboration product. This process is considered to be the rate-determining step. Moreover, the mechanism of calcium or strontium catalyzed corresponding reactions was also studied theoretically. Alternatively, DFT calculations showed that the active catalytic species is amide-metal complex, which could be generated by the carbodiimide insertion into metal-hydride bond. In this catalytic cycle, amide-metal complex reacts with borane to form a B-N bond. After the coordination of another molecular carbodiimide, a concerted hydride transfer takes place from boron to carbon, which yields the final product and regenerates the active species amide-metal. The different reaction pathway with calcium or strontium catalyzed corresponding reactions could be attributed to that the radius of calcium or strontium is larger than that of magnesium significantly. Thus, those two metals would be coordinated with an extra carbodiimide molecule, which is the precursor for the concerted hydride transfer. The DFT calculations showed that the activation free energy for the rate-determining step with calcium or strontium catalyst is much lower than that with magnesium catalyst. Therefore, a mild reaction condition might be found with calcium or strontium as catalyst for corresponding reactions.
- alkaline earth metal catalysis,
- density functional theory,
- mechanistic study,
- hydroboration
1. [1]
2. [2]
  Yaroshevsky, A. A. Geochem. Int. 2006, 44, 48. doi: 10.1134/S001670290601006X
3. [3]
  (a) Bonyhady, S. J.; Green, S. P.; Jones, C.; Nembenna, S.; Stasch, A. Angew. Chem. Int. Ed. 2009, 48, 2973. (b) Green, S. P.; Jones, C.; Stasch, A. Angew. Chem., Int. Ed. 2008, 47, 9079. (c) Arrowsmith, M.; Shepherd, W. M.; Hill, M. S.; Kociok-Kohn, G. Chem. Commun. 2014, 50, 12676. (d) Arrowsmith, M.; Hill, M. S.; Kociok-Kohn, G. Chem. Eur. J. 2015, 21, 10548. (e) Rochat, R.; Lopez, M. J.; Tsurugi, H.; Mashima, K. ChemCatChem 2016, 8, 10. (f) Arrowsmith, M.; Crimmin, M. R.; Hill, M. S.; Lomas, S. L.; Heng, M. S.; Hitchcock, P. B.; Kociok-Kohn, G. Dalton Trans. 2014, 43, 14249. (g) Barrett, A. G. M.; Crimmin, M. R.; Hill, M. S.; Hitchcock, P. B.; Procopiou, P. A. Organometallics 2007, 26, 4076.
4. [4]
5. [5]
  (a) Lampland, N. L.; Hovey, M.; Mukherjee, D.; Sadow, A. D. ACS Catal. 2015, 5, 4219. (b) Liptrot, D. J.; Hill, M. S.; Mahon, M. F.; Wilson, A. S. Angew. Chem. Int. Ed. 2015, 54, 13362. (c) Arrowsmith, M.; Hadlington, T. J.; Hill, M. S.; Kociok-Kohn, G. Chem., Commun. 2012, 48, 4567. (d) Arrowsmith, M.; Hill, M. S.; Kociok-Kohn, G. Chem. Eur. J. 2013, 19, 2776. (e) Mukherjee, D.; Ellern, A.; Sadow, A. D. Chem. Sci. 2014, 5, 959. (f) Weetman, C.; Anker, M. D.; Arrowsmith, M.; Hill, M. S.; Kociok-Köhn, G.; Liptrot, D. J.; Mahon, M. F. Chem. Sci. 2016, 7, 628. (g) Arrowsmith, M.; Hill, M. S.; Hadlington, T.; Kociok-Köhn, G.; Weetman, C. Organometallics 2011, 30, 5556.
6. [6]
  Weetman, C.; Hill, M. S.; Mahon, M. F. Chem. Eur. J. 2016, 22, 7158. doi: 10.1002/chem.201600681
7. [7]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford, CT, 2013.
8. [8]
  (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. (b) Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623. (c) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter Mater. Phys. 1988, 37, 785.
9. [9]
  (a) Francl, M. M. J. Chem. Phys. 1982, 77, 3654. (b) Hehre, W. J. J. Chem. Phys. 1972, 56, 2257. (c) Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213.
10. [10]
  (a) Dolg, M.; Stoll, H.; Preuss, H. J. Chem. Phys. 1989, 90, 1730. (b) Dolg, M.; Wedig, U.; Stoll, H.; Preuss, H. J. Chem. Phys. 1987, 86, 866.
11. [11]
  (a) Zhao, Y.; Truhlar, D. G. Acc. Chem. Res. 2008, 41, 157. (b) Qi, X.; Zhang, H.; Shao, A.; Zhu, L.; Xu, T.; Gao, M.; Liu, C.; Lan, Y. ACS Catal. 2015, 5, 6640. (c) Zhao, Y.; Truhlar, D. G. J. Chem. Phys. 2006, 125, 194101. (d) McDonald, T. M.; Mason, J. A.; Kong, X.; Bloch, E. D.; Gygi, D.; Dani, A.; Crocella, V.; Giordanino, F.; Odoh, S. O.; Drisdell, W. S.; Vlaisavljevich, B.; Dzubak, A. L.; Poloni, R.; Schnell, S. K.; Planas, N.; Lee, K.; Pascal, T.; Wan, L. F.; Prendergast, D.; Neaton, J. B.; Smit, B.; Kortright, J. B.; Gagliardi, L.; Bordiga, S.; Reimer, J. A.; Long, J. R. Nature 2015, 519, 303. (e) Jentzsch, A. V.; Emery, D.; Mareda, J.; Nayak, S. K.; Metrangolo, P.; Resnati, G.; Sakai, N.; Matile, S. Nat. Commun. 2012, 3, 905. (f) Suess, A. M.; Ertem, M. Z.; Cramer, C. J.; Stahl, S. S. J. Am. Chem. Soc. 2013, 135, 9797. (g) Li, Y. F.; Liu, Z. P.; Liu, L.; Gao, W. J. Am. Chem. Soc. 2010, 132, 13008. (h) Ferrighi, L.; Hammer, B.; Madsen, G. K. J. Am. Chem. Soc. 2009, 131, 10605.
12. [12]
  (a) Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys. 1980, 72, 650. (b) McLean, A. D.; Chandler, G. S. J. Chem. Phys. 1980, 72, 5639.
13. [13]
  (a) Li, Y.; Liu, S.; Qi, Z.; Qi, X.; Li, X.; Lan, Y. Chem. Eur. J. 2015, 21, 10131. (b) Qi, X.; Li, Y.; Zhang, G.; Li, Y.; Lei, A.; Liu, C.; Lan, Y. Dalton Trans. 2015, 44, 11165. (c) Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378. (d) Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 4538. (e) Yu, Z.; Qi, X.; Li, Y.; Liu, S.; Lan, Y. Org. Chem. Front. 2016, 3, 209.
14. [14]
  Legault, C. Y. CYLview 1.0b, Université de Sherbrooke, Canada, 2009; http://www.cylview.org.
1. [1]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
2. [2]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
3. [3]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
4. [4]
  Jiamin Li , Wenyue Zhong , Kin Shing Chan . “烯”君入瓮又入学——据元素周期表与酸碱理论谈烯烃教学. University Chemistry, 2025, 40(6): 177-182. doi: 10.12461/PKU.DXHX202408040
5. [5]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
6. [6]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
7. [7]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
8. [8]
  Tongqi Ye , Yanqing Wang , Qi Wang , Huaiping Cong , Xianghua Kong , Yuewen Ye . Reform of Classical Thermodynamics Curriculum from the Perspective of Computational Chemistry. University Chemistry, 2025, 40(7): 387-392. doi: 10.12461/PKU.DXHX202409128
9. [9]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
10. [10]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
11. [11]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
12. [12]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
13. [13]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
14. [14]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
15. [15]
  Xueting Cao , Shuangshuang Cha , Ming Gong . 电催化反应中的界面双电层：理论、表征与应用. Acta Physico-Chimica Sinica, 2025, 41(5): 100041-. doi: 10.1016/j.actphy.2024.100041
16. [16]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060
17. [17]
  Zuozhong Liang , Lingling Wei , Yiwen Cao , Yunhan Wei , Haimei Shi , Haoquan Zheng , Shengli Gao . Exploring the Development of Undergraduate Scientific Research Ability in Basic Course Instruction: A Case Study of Alkali and Alkaline Earth Metal Complexes in Inorganic Chemistry. University Chemistry, 2024, 39(7): 247-263. doi: 10.3866/PKU.DXHX202310103
18. [18]
  Baitong Wei , Jinxin Guo , Xigong Liu , Rongxiu Zhu , Lei Liu . Theoretical Study on the Structure, Stability of Hydrocarbon Free Radicals and Selectivity of Alkane Chlorination Reaction. University Chemistry, 2025, 40(3): 402-407. doi: 10.12461/PKU.DXHX202406003
19. [19]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
20. [20]
  Zhengkun QIN , Zicong PAN , Hui TIAN , Wanyi ZHANG , Mingxing SONG . A series of iridium(Ⅲ) complexes with fluorophenyl isoquinoline ligand and low-efficiency roll-off properties: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1235-1244. doi: 10.11862/CJIC.20240429

Get Citation

PDF

XML

Metrics

PDF Downloads(18)
Abstract views(1642)
HTML views(321)

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