2,6-二亚胺吡啶主族配合物的研究进展

doi:10.6023/cjoc202211037

摘要/Abstract

2,6-二亚胺基吡啶(PDI)作为具有氧化还原活性的三齿配体, 可以与过渡金属(TM)、主族元素(MG)、镧系元素和锕系元素配位. 自PDI-TM在烯烃聚合领域得到广泛应用以来, 人们对PDI配合物的合成及应用产生了浓厚的兴趣. 由于MG通常具有廉价、易得且低毒等特性, 近年来关于PDI-MG的研究发展迅速. 根据中心原子族序数的不同, 将PDI-MG配合物进行了归纳, 并对其合成方法及化学反应性进行了总结, 着重分析了不同配合物中PDI的氧化态. 当前相较于PDI-TM的研究成果、低价态PDI-MG及其催化活性的研究仍处于初始阶段, 因此对此类化合物的总结不仅有利于全面系统地了解该类化合物, 同时还有利于对新结构、新反应的开发.

关键词: 2,6-二亚胺基吡啶, 主族元素

2,6-Pyridinediimine (PDI) as a tridentate ligand with redox activity can coordinate to transition metals (TM), main group (MG) elements, lanthanides and actinides. Since the application of PDI-TM in olefin polymerization, there has been a great interest in the synthesis and application of PDI supported complexes. Due to the properties such as low cost, readily availability and low toxicity of the main group elements, the field of PDI-MG has been evolving rapidly recently. In this paper, the PDI-MG complexes are summarized according to the group number of the MG. At the same time, the synthetic methodology together with the reactivity of these reported PDI-MG complexes is summarized and the oxidation states of their ligands are emphatically analyzed. At present, compared with the development of PDI-TM, the research of low-valence PDI-MG is still in its infancy. Therefore, a comprehensive survey of these compounds could not only facilitate a comprehensive and systematic understanding of existing compounds, but also promote the development of new structures and reactivities.

Key words: 2,6-pyridinediimine, main group elements

引用此文

杨星星, 樊泳澔, 崔晶晶. 2,6-二亚胺吡啶主族配合物的研究进展[J]. 有机化学, 2023, 43(7): 2338-2350.

Xingxing Yang, Yonghao Fan, Jingjing Cui. Recent Progress in the Main Group Complexes with the 2,6-Pyridinediimine[J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2338-2350.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 28

图式1. (a)单体PDI配体的结构和(b) PDI-MG配合物的结构

Scheme 1. Conformations of (a) free PDI ligands and (b) PDI-MG complexes

图式2. (a) PDI配体的互变异构和(b) PDI配体发生烯胺互变的一个例子

Scheme 2. (a) Tautomerizations of PDI ligands, and (b) an example of enamine tautomerization in a PDI ligand

图式3. PDI配体的合成方法示例: (a)对称型和(b)非对称型

Scheme 3. Selected examples demonstrating the synthesis of (a) symmetric and (b) asymmetric PDI ligands

图式4. PDI配体的五种氧化态

Scheme 4. Five oxidation states of PDI ligands

图式5. PDI配体Δ值的计算方式

Scheme 5. Definition of Δ values for PDI ligands

(PDI)ⁿ/n	Δ_calcd/nm	Δ_exp/nm
0	0.0184	0.0185±0.002
1^－	0.0120	0.0120±0.002
2^－	0.0074	0.0065
3^－	0.0001	—
4^－	－0.0039	—

表1. Zn(II)的PDI配合物的Δ值

Table 2. Δ values of PDI-Zn(II) complexes

图式6. 化合物9和10的合成

Scheme 6. Synthesis of compounds 9 and 10

图式7. 化合物11a的合成

Scheme 7. Synthesis of compound 11a

图式8. 化合物11b, 11c和11d的合成

Scheme 8. Synthesis of compounds 11b, 11c and 11d

图式9. 化合物15~17的合成

Scheme 9. Synthesis of compounds 15~17

图式10. 化合物18a/18b, 19a/19b, 20, 21a/21b的合成

Scheme 10. Synthesis of compounds 18a/18b, 19a/19b, 20, 21a/21b

图式11. 化合物22和23的合成

Scheme 11. Synthesis of compounds 22 and 23

图式12. 化合物24~26的合成

Scheme 12. Synthesis of compounds 24~26

图式13. 化合物27的合成

Scheme 13. Synthesis of compound 27

图式14. 化合物28和29的合成

Scheme 14. Synthesis of compounds 28 and 29

图式15. 化合物30的合成

Scheme 15. Synthesis of compound 30

图式16. 化合物31的合成

Scheme 16. Synthesis of compound 31

图式17. 化合物32的合成

Scheme 17. Synthesis of compound 32

图式18. 化合物33~35的合成

Scheme 18. Synthesis of compounds 33~35

图式19. 化合物32~35的氧化态结构

Scheme 19. Oxidation state structures of compounds 32~35

图式20. 化合物37, 38, 40, 41的合成

Scheme 20. Synthesis of compounds 37, 38, 40 and 41

图式21. 化合物42~44的合成

Scheme 21. Synthesis of compounds 42~44

图式22. 化合物45~47的合成

Scheme 22. Synthesis of compounds 45~47

图式23. 化合物45~47的氧化态结构

Scheme 23. Oxidation state structures of compounds 45~47

图式24. PDI-Mg配合物的氧化/还原反应

Scheme 24. Oxidation/reduction reactions of PDI-MG complexes

图式25. 化合物18b和甲酸反应选择性脱H2和CO2的机理

Scheme 25. Mechanism of selective removal of H2 and CO2 by reaction of compound 18b with formic acid

图式26. 化合物18b插入和消除CO2

Scheme 26. Insertion and elimination of CO2 from 18b

图式27. 化合物19b激活N—H键的反应

Scheme 27. The reaction of compound 19b to activate the N—H bond

参考文献 86

[1]	Small, B. L.; Brookhart, M. J. Am. Chem. Soc. 1998, 120, 4049. doi: 10.1021/ja9802100
[2]	Flisak, Z.; Sun, W. H. ACS Catal. 2015, 5, 4713. doi: 10.1021/acscatal.5b00820
[3]	Sieh, D.; Schlimm, M.; Andernach, L.; Angersbach, F. Eur. J. Inorg. Chem. 2012, 444.
[4]	Bianchini, C.; Giambastiani, G.; Rios, I. G.; Mantovani, G.; Meli, A.; Segarra, A. M. Coord. Chem. Rev. 2006, 250, 1391. doi: 10.1016/j.ccr.2005.12.018
[5]	Bouwkamp, M. W.; Bowman, A. C.; Lobkovsky, E.; Chirik, P. J. J. Am. Chem. Soc. 2006, 128, 13340. doi: 10.1021/ja064711u pmid: 17031930
[6]	Kennedy, C. R.; Chirik, P. J. Adv. Synth. Catal. 2020, 362, 404. doi: 10.1002/adsc.201901289 pmid: 32431586
[7]	Jiao, M.; Wang, Z.; Zhang, B.; Chen, B. Z. New J. Chem. 2022, 46, 4052. doi: 10.1039/D1NJ05646H
[8]	Shejwalkar, P.; Rath, N. P.; Bauer, E. B. Synthesis 2014, 46, 57. doi: 10.1055/s-00000084
[9]	Liu, P.; Yan, M.; He, R. Appl. Organomet. Chem. 2010, 24, 131.
[10]	Chiericato, Jr. G.; Arana, C. R.; Casado, C.; Cuadrado, I.; Abruna, H. D. Inorg. Chim. Acta 2000, 32-42, 300.
[11]	Jiang, J.; Kucernak, A. Electrochim. Acta 2002, 47, 1967. doi: 10.1016/S0013-4686(02)00042-7
[12]	Fan, R. Q.; Chen, H.; Wang, P.; Yang, Y. L.; Yin, Y. B.; Hasi, W. J. Coord. Chem. 2010, 63, 1514. doi: 10.1080/00958972.2010.481715
[13]	Fan, R.; Yang, Y.; Yin, Y. Inorg. Chem. 2009, 48, 6034. doi: 10.1021/ic900339u
[14]	Shaver, M. P.; Hanhan, M. E. Chem. Commun. 2010, 46, 2127. doi: 10.1039/b922202b
[15]	Hu, X.; Li, J. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4378. doi: 10.1002/pola.26853
[16]	Perry, M. R.; Allan, L. E. Dalton Trans. 2013, 42, 9157. doi: 10.1039/c3dt32625j
[17]	Anderson, N. H.; Odoh, S. O.; Yao, Y. Nat. Chem. 2014, 6, 919. doi: 10.1038/nchem.2009
[18]	Kaim, W. Eur. J. Inorg. Chem. 2012, 343.
[19]	Bruin, B.; Bill, E.; Bothe, E. Inorg. Chem. 2000, 39, 2936. pmid: 11232835
[20]	Tidwell, J. R.; Dutton, J. L.; Martin, C. D. Dalton Trans. 2021, 50, 11716. doi: 10.1039/d1dt02085d pmid: 34612308
[21]	Bass, T. M.; Carr, C. R.; Berben, L. A. Inorg. Chem. 2020, 59, 13517. doi: 10.1021/acs.inorgchem.0c01908
[22]	Tidwell, J. R.; Martin, C. D. Organometallics 2022, 41, 1197. doi: 10.1021/acs.organomet.2c00093
[23]	Myers, T. W.; Berben, L. A. J. Am. Chem. Soc. 2013, 135, 9988. doi: 10.1021/ja4032874
[24]	Gibson, V. C.; Redshaw, C.; Solan, G. A. Chem. Rev. 2007, 107, 1745. doi: 10.1021/cr068437y
[25]	Pelascini, F.; Wesolek, M.; Peruch, F.; Lutz, P. J. Eur. J. Inorg. Chem. 2006, 4309.
[26]	Wallenhorst, C.; Kehr, G.; Luftmann, H. Organometallics 2008, 27, 6547. doi: 10.1021/om800726y
[27]	Guo, L. H.; Gao, H. Y.; Zhang, L.; Zhu, F. M.; Wu, Q. Organometallics 2010, 29, 2118. doi: 10.1021/om9010356
[28]	Kleigrewe, N.; Steffen, W.; Blömker, T.; Kehr, G.; Fröhlich, R.; Wibbeling, B.; Bazan, G. C. J. Am. Chem. Soc. 2005, 127, 13955. pmid: 16201818
[29]	Steves, J. E.; Kennedy, M. D.; Chiang, K. P. Dalton Trans. 2009, 29, 1214.
[30]	Sun, W. H.; Zhao, W.; Yu, J.; Zhang, W.; Hao, X.; Redshaw, C. Macromol. Chem. Phys. 2012, 213, 1266. doi: 10.1002/macp.201200051
[31]	Magdzinski, E.; Gobbo, P.; Martin, C. D.; Workentin, M. S.; Ragogna, P. J. Inorg. Chem. 2012, 51, 8425. doi: 10.1021/ic300974u pmid: 22775510
[32]	Orrell, K. G.; Osborne, A. G.; Šik, V. Organomet. Chem. 1997, 530, 235. doi: 10.1016/S0022-328X(96)06661-2
[33]	Reeske, G.; Cowley, A. H. Chem. Commun. 2006, 46, 4856.
[34]	Martin, C. D.; Ragogna, P. J. Inorg. Chem. 2012, 51, 2947. doi: 10.1021/ic202213x pmid: 22339169
[35]	Martin, C. D.; Ragogna, P. J. Dalton Trans. 2011, 40, 11976. doi: 10.1039/c1dt11111f pmid: 21983569
[36]	Reardon, D.; Conan, F.; Gambarotta, S.; Yap, G.; Wang, Q. J. Am. Chem. Soc. 1999, 121, 9318. doi: 10.1021/ja990263x
[37]	Ionkin, A. S.; Marshall, W. J.; Adelman, D. J.; Fones, B. B.; Fish, B. M.; Schiffhauer, M. F.; Soper, P. D.; Waterland, R. L.; Spence, R. E.; Xie, T. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 585. doi: 10.1002/(ISSN)1099-0518
[38]	Small, B. L.; Brookhart, M.; Bennett, A. M. J. Am. Chem. Soc. 1998, 120, 4049. doi: 10.1021/ja9802100
[39]	Britovsek, G. J. P.; Gibson, V. C.; McTavish, S. J.; Solan, G. A.; White, A. J. P.; Williams, D. J.; Maddox, P. J. Chem. Commun. 1998, 7, 849.
[40]	Ma, Z.; Sun, W. H.; Li, Z. L.; Shao, C. X.; Hu, Y. L.; Li, X. H. Polym. Int. 2002, 51, 994. doi: 10.1002/(ISSN)1097-0126
[41]	Bart, S. C.; Chłopek, K.; Bill, E.; Bouwkamp, M. W.; Lobkovsky, E.; Chirik, P. J. J. Am. Chem. Soc. 2006, 128, 13901. doi: 10.1021/ja064557b
[42]	Knijnenburg, Q.; Gambarotta, S.; Budzelaar, P. H. Dalton Trans. 2006, 46, 5442.
[43]	Römelt, C.; Weyhermüller, T.; Wieghardt, K. Coord. Chem. Rev. 2019, 380, 287. doi: 10.1016/j.ccr.2018.09.018
[44]	Brown, S. N. Inorg. Chem. 2012, 51, 1251. doi: 10.1021/ic202764j pmid: 22260321
[45]	Enright, D.; Gambarotta, S.; Yap, G. P.; Budzelaar, P. H. Angew. Chem., Int. Ed. 2002, 41, 3873. doi: 10.1002/1521-3773(20021018)41:20【-逻辑与-】lt;3873::AID-ANIE3873【-逻辑与-】gt;3.0.CO;2-8
[46]	Myers, T. W.; Sherbow, T. J.; Fettinger, J. C.; Berben, L. A. Dalton Trans. 2016, 45, 5989. doi: 10.1039/C5DT01541C
[47]	Addison, A. W.; Rao, T. N.; Reedijk, J.; Verschoor, G. C. J. Chem. Soc., Dalton Trans. 1984, 1349.
[48]	Arrowsmith, M.; Hill, M. S.; Kociok-Köhn, G. Organometallics 2010, 29, 4203. doi: 10.1021/om100649z
[49]	Dawkins, M. J. C.; Simonov, A. N.; Jones, C. Dalton Trans. 2020, 49, 6627. doi: 10.1039/D0DT01278E
[50]	Dawson, K.; Mallov, I.; Burchell, T.; Yap, G. P.; Richeson, D. S. Dalton Trans. 2010, 39, 1266. doi: 10.1039/B920047A
[51]	Jurca, T.; Lummiss, J.; Burchell, T. J.; Gorelsky, S. I.; Richeson, D. S. J. Am. Chem. Soc. 2009, 131, 4608. doi: 10.1021/ja901128q
[52]	Thompson, E. J.; Myers, T. W.; Berben, L. A. Angew. Chem., Int. Ed. Engl. 2014, 53, 14132. doi: 10.1002/anie.v53.51
[53]	Andrews, C. G.; Macdonald, C. L. B. Angew. Chem., Int. Ed. 2005, 44, 7453. doi: 10.1002/(ISSN)1521-3773
[54]	Cooper, B. F. T.; Macdonald, C. L. B. J. Organomet. Chem. 2008, 693, 1707. doi: 10.1016/j.jorganchem.2007.10.040
[55]	Hill, M. S.; Hitchcock, P. B. Chem. Commun. 2004, 16, 1818.
[56]	Jones, C.; Junk, P. C.; Platts, J. A.; Rathmann, D.; Stasch, A. Dalton Trans. 2005, 2497.
[57]	Baba, T.; Takeuchi, M.; Nakai, H. Chem. Phys. Lett. 2006, 424, 193. doi: 10.1016/j.cplett.2006.03.098
[58]	Jurca, T.; Korobkov, I.; Gorelsky, S. I.; Richeson, D. S. Inorg. Chem. 2013, 52, 5749. doi: 10.1021/ic302552v
[59]	Cordero, B.; Gomez, V.; Reves, M.; Echeverria, J.; Cremades, E.; Barragan, F.; Alvarez, S. Dalton Trans. 2008, 21, 2832.
[60]	Simon, S.; Duran, M.; Dannenberg, J. J. J. Chem. Phys. 1996, 105, 11024. doi: 10.1063/1.472902
[61]	Mayer, I. Int. J. Quantum Chem. 1986, 29, 73. doi: 10.1002/(ISSN)1097-461X
[62]	Reger, D. L.; Wright, T. D.; Smith, M. D.; Rheingold, A. L.; Kassel, S.; Concolino, T.; Rhagitan, B. Polyhedron 2002, 21, 1795. doi: 10.1016/S0277-5387(02)01058-6
[63]	Bailey, N. A.; Fenton, D. E.; Jackson, I. T.; Moody, R.; Barbarin, L. R. J. Chem. Soc., Chem. Commun. 1983, 23, 1462.
[64]	Harrowfield, J. M.; Miyamae, H.; Shand, T. M.; Skelton, B. W.; Soudi, A. A.; White, A. H. Aust. J. Chem. 1996, 49, 1051. doi: 10.1071/CH9961051
[65]	Soleilhavoup, M.; Bertrand, G. Chem 2020, 6, 1275. doi: 10.1016/j.chempr.2020.04.015
[66]	Schäfer, A.; Saak, W.; Haase, D.; Müller, T. Chem.-Eur. J. 2009, 15, 3945. doi: 10.1002/chem.v15:16
[67]	Singh, A. P.; Roesky, H. W.; Carl, E.; Stalke, D.; Demers, J. P.; Lange, A. J. Am. Chem. Soc. 2012, 134, 4998. doi: 10.1021/ja300563g
[68]	Flock, J.; Suljanovic, A.; Torvisco, A.; Schoefberger, W.; Gerke, B.; Pöttgen, R.; Fischer, R. C.; Flock, M. Chem.-Eur. J. 2013, 19, 15504. doi: 10.1002/chem.v19.46
[69]	Bart, S. C.; Chłopek, K.; Bill, E.; Wieghardt, K.; Chirik, P. J. J. Am. Chem. Soc. 2006, 128, 13901. doi: 10.1021/ja064557b
[70]	Khan, S.; Michel, R.; Dieterich, J. M.; Mata, R. A.; Roesky, H. W.; Demers, J. P.; Lange, A.; Stalke, D. J. Am. Chem. Soc. 2011, 133, 17889. doi: 10.1021/ja207538g
[71]	Zabula, A. V.; Pape, T.; Hepp, A. J. Am. Chem. Soc. 2008, 130, 5648. doi: 10.1021/ja801000b
[72]	Power, P. P. Nature 2010, 463, 171. doi: 10.1038/nature08634
[73]	Chu, T.; Belding, L.; Dudding, T.; Korobkov, I.; Nikonov, G. I. Angew. Chem., Int. Ed. 2014, 53, 2711. doi: 10.1002/anie.201309421
[74]	Lippens, P. E. Phys. Rev. B 1999, 60, 4576. doi: 10.1103/PhysRevB.60.4576
[75]	Greb, L. Eur. J. Inorg. Chem. 2022, e202100871.
[76]	Reeske, G.; Cowley, A. H. Chem. Commun. (Camb.) 2006, 16, 1784.
[77]	Yap, G. P. A.; Gambarotta, S. private communication to CCDC (no. 116252), 1999.
[78]	Chitnis, S. S.; LaFortune, J. H.; Cummings, H.; Liu, L. L.; Andrews, R.; Stephan, D. W. Organometallics 2018, 37, 4540. doi: 10.1021/acs.organomet.8b00686
[79]	Gray, P. A.; Braun, J. D.; Rahimi, N.; Herbert, D. E. Eur. J. Inorg. Chem. 2020, 2105.
[80]	Martin, C. D.; Jennings, M. C.; Ferguson, M. J.; Ragogna, P. J. Angew. Chem., Int. Ed. 2009, 48, 2210. doi: 10.1002/anie.200805198 pmid: 19137516
[81]	Pyykkö, P.; Atsumi, M. Chem.-Eur. J. 2009, 15, 186. doi: 10.1002/chem.200800987 pmid: 19058281
[82]	Mantina, M.; Chamberlin, A. C.; Valero, R.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. A 2009, 113, 5806. doi: 10.1021/jp8111556
[83]	Martin, C. D.; Le, C. M.; Ragogna, P. J. J. Am. Chem. Soc. 2009, 131, 15126. doi: 10.1021/ja9073968 pmid: 19803516
[84]	Bonyhady, S. J.; Jones, C.; Nembenna, S.; Stasch, A.; Edwards, A. J.; McIntyre, G. J. Chem.-Eur. J. 2010, 16, 938. doi: 10.1002/chem.200902425 pmid: 19950340
[85]	Hicks, J.; Juckel, M.; Paparo, A.; Dange, D.; Jones, C. Organometallics 2018, 37, 4810. doi: 10.1021/acs.organomet.8b00803
[86]	Myers, T. W.; Berben, L. A. Chem. Sci. 2014, 5, 2771. doi: 10.1039/C4SC01035C