1478
Di Meng et al. / Chinese Journal of Catalysis 41 (2020) 1474–1479
[5] K. Shimomaki, K. Murata, R. Martin, N. Iwasawa, J. Am. Chem. Soc.,
2017, 139, 9467–9470.
[6] D. Koyama, H. J. A. Dale, A. J. Orr-Ewing, J. Am. Chem. Soc., 2018,
140, 1285–1293.
[7] M. Goez, C. Kerzig, R. Naumann, Angew. Chem. Int. Ed., 2014, 53,
9914–9916.
[8] I. Ghosh, B. Konig, Angew. Chem. Int. Ed., 2016, 55, 7676–7679.
[9] C. Y. Sun, D. Zhao, C. C. Chen, W. H. Ma, J. C. Zhao, Environ. Sci.
Technol., 2009, 43, 157–162.
Chem. Soc., 2014, 136, 2162–2167.
[23] S. E. Creutz, K. J. Lotito, G. C. Fu, J. C. Peters, Science, 2012, 338,
647–651.
[24] T. P. Nicholls, J. C. Robertson, M. G. Gardiner, A. C. Bissember,
Chem. Commun., 2018, 54, 4589–4592.
[25] J. C. Theriot, C. H. Lim, H. Yang, M. D. Ryan, C. B. Musgrave, G. M.
Miyake, Science, 2016, 352, 1082–1086.
[26] M. Haring, R. Perez-Ruiz, A. Jacobi von Wangelin, D. D. Diaz, Chem.
Commun., 2015, 51, 16848–16851.
[10] L. N. Li, W. Chang, Y. Wang, H. W. Ji, C. C. Chen, W. H. Ma, J. C. Zhao,
Chem.-Eur. J., 2014, 20, 11163–11170.
[27] R. Matsubara, T. Yabuta, U. M. Idros, M. Hayashi, F. Ema, Y. Kobori,
K. Sakata, J. Org. Chem., 2018, 83, 9381–9390.
[11] W. Chang, C. Y. Sun, X. B. Pang, H. Sheng, Y. Li, H. W. Ji, W. J. Song, C.
C. Chen, W. H. Ma, J. C. Zhao, Angew. Chem. Int. Ed., 2015, 54,
2052–2056.
[12] Y. H. Lv, X. F. Cao, H. Y. Jiang, W. J. Song, C. C. Chen, J. C. Zhao, Appl.
Catal. B, 2016, 194, 150–156.
[13] Q. Zhu, Y. Y. Wang, H. N. Zhang, R. Duan, C. C. Chen, W. J. Song, J. C.
Zhao, Appl. Catal. B, 2017, 219, 322–328.
[14] Y. Y. Wang, Q. Zhu, Y. Wei, Y. J. Gong, C. C. Chen, W. J. Song, J. C.
Zhao, Appl. Catal. B, 2018, 231, 262–268.
[15] J. Z. Lu, N. S. Khetrapal, J. A. Johnson, X. C. Zeng, J. Zhang, J. Am.
Chem. Soc., 2016, 138, 15805–15808.
[16] S. M. Senaweera, A. Singh, J. D. Weaver, J. Am. Chem. Soc., 2014,
136, 3002–3005.
[28] J. T. Shang, H. Y. Tang, H. W. Ji, W. H. Ma, C. C. Chen, J. C. Zhao, Chin.
J. Catal., 2017, 38, 2094–2101.
[29] B. Liu, C. H. Lim, G. M. Miyake, J. Am. Chem. Soc., 2017, 139,
13616–13619.
[30] S. V. Rosokha, E. A. Loboda, J. Phys. Chem. A, 2015, 119,
3833–3842.
[31] C. G. S. Lima, T. D. Lima, M. Duarte, I. D. Jurberg, M. W. Paixao, ACS
Catal., 2016, 6, 1389–1407.
[32] in Principles of Fluorescence Spectroscopy (Ed.: J. R. Lakowicz),
Springer US, Boston, MA, 2006, pp. 277–330.
[33] A. Banerjee, D. E. Falvey, J. Org. Chem., 1997, 62, 6245–6251.
[34] Z. Chami, M. Gareil, J. Pinson, J. M. Saveant, A. Thiebault, J. Org.
Chem., 1991, 56, 586–595.
[17] M. B. Khaled, R. K. El Mokadem, J. D. Weaver, J. Am. Chem. Soc.,
2017, 139, 13092–13101.
[35] M. Lei, S. Guo, Z. Y. Wang, L. H. Zhu, H. Q. Tang, Environ. Sci. Tech-
nol., 2018, 52, 11743–11751.
[18] C. Costentin, M. Robert, J. M. Saveant, J. Am. Chem. Soc., 2004, 126,
16051–16057.
[19] J. D. Nguyen, E. M. D'Amato, J. M. R. Narayanam, C. R. J. Stephenson,
Nat. Chem., 2012, 4, 854–859.
[36] Y. Wei, Y. J. Gong, X. Zhao, Y. Y. Wang, R. Duan, C. C. Chen, W. J.
Song, J. C. Zhao, Environ.-Sci. Nano, 2019, 6, 1585–1593.
[37] H. Sakamoto, J. Imai, Y. Shiraishi, S. Tanaka, S. Ichikawa, T. Hirai,
ACS Catal., 2017, 7, 5194–5201.
[20] H. L. Yin, Y. Jin, J. E. Hertzog, K. C. Mullane, P. J. Carroll, B. C. Manor,
J. M. Anna, E. J. Schelter, J. Am. Chem. Soc., 2016, 138,
16266–16273.
[21] L. Pause, M. Robert, J. M. Saveant, J. Am. Chem. Soc., 1999, 121,
7158–7159.
[38] K. Fuku, K. Hashimoto, H. Kominami, Chem. Commun., 2010, 46,
5118–5120.
[39] M. Lei, N. Wang, L. H. Zhu, H. Q. Tang, Chemosphere, 2016, 150,
536–544.
[40] Z. Hu, X. Wang, H. T. Dong, S. Y. Li, X. K. Li, L. S. Li, J. Hazard. Mater.,
2017, 340, 1–15.
[22] H. Q. Do, S. Bachman, A. C. Bissember, J. C. Peters, G. C. Fu, J. Am.
基于芳香胺化合物的光催化脱卤加氢
孟 涤a,b,†, 朱 倩a,b,†,‡, 魏 燕a,b, 甄胜利c, 段 苒a, 陈春城a,b, 宋文静a,b,*, 赵进才a,b
a中国科学院化学研究所光化学重点实验室, 中国科学院分子科学科教融合卓越中心, 北京100190
b中国科学院大学, 北京100049
c北京高能时代环境技术股份有限公司, 北京100095
摘要: 近年来, 光催化活化碳卤键已经成为构筑新化学键的有力方法. 其基本原理在于利用光激发产生的高活性激发态或
中间物种, 经由电子转移过程实现碳卤键的断裂产生碳自由基和卤离子(C–X + e → C• + X–). 碳自由基通过加氢或者或
亲电进攻等途径完成反应, 实现碳卤键到碳氢、碳碳等化学键的转化. 目前已报道的用于活化碳卤键的光催化剂包括过渡
金属(如钌、铱)配合物, 过渡金属盐(CeIIICl63–)、有机小分子光(二氢苯二嗪、苯基吩噻嗪、苝酰亚胺以及芘类衍生物分子)
等.
本工作中我们开发了基于小分子芳香胺, 包括N,N,N’,N’-四甲基对苯二胺(TMPD)与N,N,N’,N’-四甲基联苯胺(TMB)
等作为光催化剂实现高惰性芳香卤代化合物脱卤加氢的催化体系. 荧光强度/寿命测试表明芳香胺的强还原性单重激发态
可通过扩散控制的电子转移实现惰性卤代底物(氯苯, 六氟苯等)中碳卤键的解离;并且原位顺磁共振直接观察到了这一
步骤产生的芳基自由基以及TMPD正离子自由基; 自由基捕获实验也为解离电子转移活化碳卤键提供了进一步的支持.
芳香胺分子在计量反应条件下可同时作为光敏剂和电子/氢给体可在紫外光照下(λ > 360 nm)实现芳香卤代化合物的
脱卤加氢, 并表现出较高的转化率和选择性:溴苯乙酮(86%, 90%)、六氟苯(91%, 五氟苯26%/1,2,4,5-四氟苯17%)、氯苯(63%,
80%). 引入N,N二异丙基乙二胺(DIPEA)作为电子给体, 能够还原芳香胺正离子自由基完成催化剂循环, DIPEA同时作为