低配位含磷官能团的研究进展

doi:10.12461/PKU.DXHX202409144

摘要/Abstract

摘要： 官能团是分子组成的重要构筑基元，决定着分子的物理化学性质。对官能团的结构、性质和功能的研究是合成化学最核心的内容，进而构筑了现代合成化学的理论体系。在“发现和创造新物质”这一化学学科核心工作中，设计和开发新型官能团尤为重要。随着合成技术的进步，逐渐出现了一些含P、B、S、Si等新型官能团的报道。基于对角线规则，含磷官能团可能会表现出类似含碳官能团的性质。同时，磷元素的引入还将进一步调节官能团的位阻和电子性质，从而展现出其独特的物理化学性质和应用潜力。本文综述了近年来低配位含磷官能团，如磷炔、双磷分子、磷宾、磷烯、双磷烯、磷杂苯等的研究进展，并对该领域未来的发展方向进行展望。

关键词: 含磷官能团, 对角线规则, 有机磷, 低配位磷

Abstract: Functional groups are essential molecular building blocks that govern the physicochemical properties of molecules. The study of their structure, properties, and functions is central to synthetic chemistry, forming the foundation of modern synthetic chemistry theories. In the pursuit of discovering and creating new substances, the design and development of novel functional groups is of particular importance. With advancements in synthetic technology, new functional groups containing main-group elements such as phosphorus (P), boron (B), sulfur (S), and silicon (Si) have been reported. According to the diagonal rule, phosphorus-containing functional groups can exhibit properties similar to their carbon-containing counterparts. Moreover, the introduction of phosphorus atoms can further modulate the steric and electronic properties of these groups, revealing distinctive physicochemical characteristics and broad application potential. This review summarizes recent developments in low-coordinated phosphorus-containing functional groups, such as phosphaalkynes, diphosphorus compounds, phosphinidenes, phosphaalkenes, diphosphenes, and phosphinines, and discusses the future directions for research in this field.

Key words: Phosphorus-containing functional groups, Diagonal rule, Organophosphorus, Low-coordinated phosphorus

蒋文, 林洁丽, 李忠曙. 低配位含磷官能团的研究进展[J]. 大学化学, 2025, 40(8): 138-151.

Wen Jiang, Jieli Lin, Zhongshu Li. Recent Advances in Low-Coordinated Phosphorus-Containing Functional Groups[J]. University Chemistry, 2025, 40(8): 138-151.

链接本文: https://www.dxhx.pku.edu.cn/CN/10.12461/PKU.DXHX202409144

https://www.dxhx.pku.edu.cn/CN/Y2025/V40/I8/138

参考文献

[1] Xu, G.; Senanayake, C. H.; Tang, W. Acc. Chem. Res. 2019, 52, 1101.
[2] Kutzelnigg, W. Angew. Chem. Int. Ed. Engl. 1984, 23, 272.
[3] Dillon, K. B.; Mathey, F.; Nixon, J. F. Phosphorus: The Carbon Copy: From Organophosphorus to Phospha-organic Chemistry; Wiley: West Sussex, UK, 1998.
[4] Mathey, F.; Duan, Z. Sci. Sin. Chim. 2010, 40, 888.
[5] Laurent, J. C. T. R. B.-S.; King, M. A.; Kroto, H. W.; Nixon, J. F.; Suffolk, R. J. J. Chem. Soc. Dalton Trans. 1983, 755.
[6] Bani-Fwaz, M. Z. J. Coord. Chem. 2020, 73, 887.
[7] Chirila, A.; Wolf, R.; Chris Slootweg, J.; Lammertsma, K. Coord. Chem. Rev. 2014, 270–271, 57.
[8] Gier, T. E. J. Am. Chem. Soc. 1961, 83, 1769.
[9] Hopkinson, M. J.; Kroto, H. W.; Nixon, J. F.; Simmons, N. P. C. J. Chem. Soc. Chem. Commun. 1976, 513.
[10] Regitz, M. Chem. Rev. 1990, 90, 191.
[11] Becker, G.; Gresser, G.; Uhl, W. Z. Naturforsch. B 1981, 36, 16.
[12] Markl, G.; Sejpka, H. Tetrahedron Lett. 1985, 26, 5507.
[13] Laurent, J. C. T. R. B. S.; Cooper, T. A.; Kroto, H. W.; Nixon, J. F.; Ohashi, O.; Ohno, K. J. Mol. Struct. 1982, 79, 215.
[14] Kroto, H. W.; Nixon, J. F.; Simmons, N. P. C. J. Mol. Spectrosc. 1980, 82, 185.
[15] Kroto, H. W.; Nixon, J. F.; Simmons, N. P. C. J. Mol. Spectrosc. 1979, 77, 270.
[16] Karaghiosoff, K.; Schmidpeter, A. Phosphorus, Sulfur Relat. Elem. 1988, 36, 217.
[17] Nixon, J. F. Chem. Rev. 1988, 88, 1327.
[18] Guillemin, J.-C.; Janati, T.; Denis, J.-M. J. Org. Chem. 2001, 66, 7864.
[19] Transue, W. J.; Yang, J.; Nava, M.; Sergeyev, I. V.; Barnum, T. J.; McCarthy, M. C.; Cummins, C. C. J. Am. Chem. Soc. 2018, 140, 17985.
[20] Benson, S. W. J. Chem. Educ. 1965, 42, 502.
[21] Bock, H.; Mueller, H. Inorg. Chem. 1984, 23, 4365.
[22] Piro, N. A.; Figueroa, J. S.; McKellar, J. T.; Cummins, C. C. Science 2006, 313, 1276.
[23] Velian, A.; Nava, M.; Temprado, M.; Zhou, Y.; Field, R. W.; Cummins, C. C. J. Am. Chem. Soc. 2014, 136, 13586.
[24] Eckhardt, A. K.; Riu, M.-L. Y.; Ye, M.; Müller, P.; Bistoni, G.; Cummins, C. C. Nat. Chem. 2022, 14, 928.
[25] Wang, S.; Sears, J. D.; Moore, C. E.; Rheingold, A. L.; Neidig, M. L.; Figueroa, J. S. Science 2022, 375, 1393.
[26] Xu, L. T.; Dunning, T. H. J. Chem. Theo. Comput. 2015, 11, 2496.
[27] Nesterov, V.; Reiter, D.; Bag, P.; Frisch, P.; Holzner, R.; Porzelt, A.; Inoue S. Chem. Rev. 2018, 118, 9678.
[28] Hirai, K.; Itoh, T.; Tomioka, H. Chem. Rev. 2009, 109, 3275.
[29] Iwamoto, E.; Hirai, K.; Tomioka, H. J. Am. Chem. Soc. 2003, 125, 14664.
[30] Tomioka, H.; Iwamoto, E.; Itakura H.; Hirai, K. Nature 2001, 412, 626.
[31] Benkő, Z.; Streubel, R.; Nyulászi, L. Dalton Trans. 2006, 4321.
[32] Li, X.; Lei, D.; Chiang, M. Y.; Gaspar, P. P. J. Am. Chem. Soc. 1992, 114, 8526.
[33] Li, X.; Weissman, S. I.; Lin, T.-S.; Gaspar, P. P.; Cowley, A. H.; Smirnov, A. I. J. Am. Chem. Soc. 1994, 116, 7899.
[34] Akimov, A. V.; Ganushevich, Y. S.; Korchagin, D. V.; Miluykov, V. A.; Misochko, E. Y. Angew. Chem. Int. Ed. 2017, 56, 7944.
[35] Nguyen, M. T.; Van Keer, A.; Vanquickenborne, L. G. J. Org. Chem. 1996, 61, 7077.
[36] Liu, L.; Ruiz, D. A.; Munz, D.; Bertrand, G. Chem 2016, 1, 147.
[37] Luo, Q.; Liu, T.; Huang, L.; Yang, C.; Lu, W. Angew. Chem. Int. Ed. 2024, 63, e202405122.
[38] Chen, Y.; Su, P.; Wang, D.; Ke, Z.; Tan, G. Nat. Commun. 2024, 15, 4579.
[39] Liu, L. L.; Zhou, J.; Andrews, R.; Stephan, D. W. J. Am. Chem. Soc. 2018, 140, 7466.
[40] Riu, M.-L. Y.; Eckhardt, A. K.; Cummins, C. C. J. Am. Chem. Soc. 2022, 144, 7578.
[41] Saint-Denis, T. G.; Wheeler, T. A.; Chen, Q.; Balázs, G.; Settineri, N. S.; Scheer, M.; Tilley, T. D. J. Am. Chem. Soc. 2024, 146, 4369.
[42] van Eis, M. J.; Zappey, H.; de Kanter, F. J. J.; de Wolf, W. H.; Lammertsma, K.; Bickelhaupt, F. J. Am. Chem. Soc. 2000, 122, 3386.
[43] Velian, A.; Cummins, C. C. J. Am. Chem. Soc. 201, 134, 13978.
[44] Schmidt, M. W.; Truong, P. N.; Gordon, M. S. J. Am. Chem. Soc. 1987, 109, 5217.
[45] Recker, G. Z. Anorg. Allg. Chem. 1976, 423, 242.
[46] Ziółkowska, A.; Doroszuk, J.; Ponikiewski, Ł. Organometallics 2023, 42, 505.
[47] Klebach, T. C.; Lourens, R.; Bickelhaupt, F. J. Am. Chem. Soc. 1978, 100, 4886.
[48] Hibbs, D. E.; Jones, C.; Richards, A. F. J. Chem. Soc. Dalton Trans. 1999, 3531.
[49] Romanenko, V.; Ruban, A.; Povolotskii, M.; Polyachenko, L.; Markovskii, L. Zh. Org. Khim. 1986, 56, 1186.
[50] Appel, R.; Immenkeppel, M. Z. Anorg. Allg. Chem. 1987, 553, 7.
[51] Yam, M.; Chong, J. H.; Tsang, C.-W.; Patrick, B. O.; Lam, A. E.; Gates, D. P. Inorg. Chem. 2006, 45, 5225.
[52] Shah, S.; Protasiewicz, J. D. Chem. Commun. 1998, 1585.
[53] Breen, T. L.; Stephan, D. W. J. Am. Chem. Soc. 1995, 117, 11914.
[54] Masuda, J. D.; Jantunen, K. C.; Ozerov, O. V.; Noonan, K. J. T.; Gates, D. P.; Scott, B. L.; Kiplinger, J. L. J. Am. Chem. Soc. 2008, 130, 2408.
[55] Lacombe, S.; Gonbeau, D.; Cabioch, J. L.; Pellerin, B.; Denis, J. M.; Pfister-Guillouzo, G. J. Am. Chem. Soc. 1988, 110, 6964.
[56] Weber, L. Eur. J. Inorg. Chem. 2000, 2000, 2425.
[57] Meriem, A.; Majoral, J.-P.; Revel, M.; Navech, J. Tetrahedron Lett. 1983, 24, 1975.
[58] Köhler, H.; Michaelis, A. Ber. Dtsch. Chem. Ges. 1877, 10, 807.
[59] Daly, J. J.; Maier, L. Nature 1964, 203, 1167.
[60] Daly, J. J.; Maier, L. Nature 1965, 208, 383.
[61] Yoshifuji, M.; Shima, I.; Inamoto, N.; Hirotsu, K.; Higuchi, T. J. Am. Chem. Soc. 1981, 103, 4587.
[62] Caminade, A.-M.; Verrier, M.; Ades, C.; Paillous, N.; Koenig, M. J. Chem. Soc. Chem. Commun. 1984, 875.
[63] Masaaki, Y.; Takahiro, S.; Naoki, I. Chem. Lett. 1988, 17, 1735.
[64] Asami, S.-S.; Okamoto, M.; Suzuki, K.; Yamashita, M. Angew. Chem. Int. Ed. 2016, 55, 12827.
[65] Smit, C. N.; van der Knaap, T. A.; Bickelhaupt, F. Tetrahedron Lett. 1983, 24, 2031.
[66] Liu, L. L.; Ruiz, D. A.; Dahcheh, F.; Bertrand, G.; Suter, R.; Tondreau, A. M.; Grützmacher, H. Chem. Sci. 2016, 7, 2335.
[67] Escudie, J.; Couret, C.; Ranaivonjatovo, H.; Satgé, J. J. Chem. Soc. Chem. Commun. 1984, 1621.
[68] Yoshifuji, M.; Shibayama, K.; Inamoto, N.; Matsushita, T.; Nishimoto, K. J. Am. Chem. Soc. 1983, 105, 2495.
[69] Doddi, A.; Bockfeld, D.; Zaretzke, M.-K.; Kleeberg, C.; Bannenberg, T.; Tamm, M. Dalton Trans. 2017, 46, 15859.
[70] Niecke, E.; Altmeyer, O.; Nieger, M. Angew. Chem. Int. Ed. 1991, 30, 1136.
[71] Romanenko, V. D.; Ruban, A. V.; Iksanova, S. V.; Polyachenko, L. K.; Markovski, L. N. Phosphorus, Sulfur Relat. Elem. 1985, 22, 365.
[72] Markovski, L. N.; Romanenko, V. D.; Ruban, A. V. Phosphorus, Sulfur Relat. Elem. 1987, 30, 447.
[73] Liu, L. L.; Cao, L. L.; Zhou, J.; Stephan, D. W. Angew. Chem. Int. Ed. 2019, 58, 273.
[74] Niecke, E.; Kramer, B.; Nieger, M. Angew. Chem. Int. Ed. 1989, 28, 215.
[75] Weber, L.; Ebeler, F.; Ghadwal, R. S. Coord. Chem. Rev. 2022, 461, 214499.
[76] Lin, J.; Liu, S.; Zhang, J.; Grützmacher, H.; Su, C.-Y.; Li, Z. Chem. Sci. 2023, 14, 10944.
[77] Weber, L. Chem. Rev. 1992, 92, 1839.
[78] Wong, T. C.; Bartell, L. S. J. Chem. Phys. 1974, 61, 2840.
[79] Baldridge, K. K.; Gordon, M. S. J. Am. Chem. Soc. 1988, 110, 4204.
[80] Nyulászi, L.; Keglevich, G. Heteroat. Chem. 1994, 5, 131.
[81] Zhang, J.; Li, Y.; Liu, S.; Lin, J.; Fan, Y.-N.; Li, Z. Eur. J. Inorg. Chem. 2023, 26, e202300595.
[82] Zhang, J.; Hou, Y.; Liu, S.; Lin, J.; Li, Z. Dalton Trans. 2024, 53, 5608.
[83] Hou, Y.; Li, Z.; Li, Y.; Liu, P.; Su, C.-Y.; Puschmann, F.; Grützmacher, H. Chem. Sci. 2019, 10, 3168.
[84] Chen, X.; Li, Z.; Grützmacher, H. Chem. Eur. J. 2018, 24, 8432.
[85] Müller, C.; Broeckx, L. E. E.; de Krom, I.; Weemers, J. J. M. Eur. J. Inorg. Chem. 2013, 2013, 187.
[86] Coles, N. T.; Sofie Abels, A.; Leitl, J.; Wolf, R.; Grützmacher, H.; Müller, C. Coord. Chem. Rev. 2021, 433, 213729.
[87] Müller, C.; Vogt, D. Phosphorus Compounds: Advanced Tools in Catalysis and Material Sciences; Peruzzini, M., Gonsalvi, L. Eds.; Springer: Dordrecht, Netherlands, 2011; p. 151.
[88] Müller, C.; Vogt, D. Dalton Trans. 2007, 5505.
[89] Märkl, G. Angew. Chem. Int. Ed. 1966, 5, 846.
[90] Carrasco, A. C.; Pidko, E. A.; Masdeu-Bultó, A. M.; Lutz, M.; Spek, A. L.; Vogt, D.; Müller, C. New J. Chem. 2010, 34, 1547.
[91] Müller, C.; Pidko, E. A.; Staring, A. J. P. M.; Lutz, M.; Spek, A. L.; van Santen, R. A.; Vogt, D. Chem. Eur. J. 2008, 14, 4899.
[92] Müller, C.; Pidko, E. A.; Totev, D.; Lutz, M.; Spek, A. L.; van Santen, R. A.; Vogt, D. Dalton Trans. 2007, 5372.
[93] Müller, C.; Pidko, E. A.; Lutz, M.; Spek, A. L.; Vogt, D. Chem. Eur. J. 2008, 14, 8803.
[94] Ashe, A. J. III. J. Am. Chem. Soc. 1971, 93, 3293.
[95] Mulliken, R. S. J. Am. Chem. Soc. 1950, 72, 4493.
[96] Rösch, W.; Regitz, M. Z. Naturforsch. B 1986, 41, 931.
[97] Chen, X.; Alidori, S.; Puschmann, F. F.; Santiso-Quinones, G.; Benkő, Z.; Li, Z.; Becker, G.; Grützmacher, H.-F.; Grützmacher, H. Angew. Chem. Int. Ed. 2014, 53, 1641.
[98] Avarvari, N.; Le Floch, P.; Mathey, F. J. Am. Chem. Soc. 1996, 118, 11978.
[99] Avarvari, N.; Le Floch, P.; Charrier, C.; Mathey, F. Heteroat. Chem. 1996, 7, 397.
[100] Nakajima, K.; Takata, S.; Sakata, K.; Nishibayashi, Y. Angew. Chem. Int. Ed. 2015, 54, 7597.