SIOC English
有机化学
高级检索

有机化学 >

0 1

DOI: https://doi.org/10.6023/cjoc202506023

硅杂环丙烯的合成和表征

  • 陈艺林 ,
  • 岳佳怡 ,
  • 林依鸣 ,
  • 刘兵妮 ,
  • 戴闻 ,
  • 朱红平
展开
  • a表界面化学全国重点实验室, 厦门大学化学化工学院 厦门 361005;
    b江苏南大光电股份有限公司, 苏州 210046

收稿日期: 2025-06-17

  修回日期: 2025-08-04

  网络出版日期: 2025-09-24

基金资助

国家自然科学基金面上项目21972112和福建省产学研项目2021H6002.

收起

Synthesis and Characterization of Silacyclopropenes

  • Yilin Chen ,
  • Jiayi Yue ,
  • Yiming Lin ,
  • Bingni Liu ,
  • Wen Dai ,
  • Hongping Zhu
Expand
  • aState Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005;
    bJiangsu Nata Opto-electronic Material Co., Ltd., Soochow, 210046
†Yilin Chen, Jiayi Yue, and Yiming Lin contributed equally to this work.

Received date: 2025-06-17

  Revised date: 2025-08-04

  Online published: 2025-09-24

Supported by

National Natural Science Foundation of China (No. 21972112) and Productive Research Program of Fujian Province (2021H6002).

Fold

摘要

合成了氯代硅宾化合物L(Cl)Si (1, L = PhC(NtBu)2). 1分别与HC≡CPPh2、PhC≡CPPh2、Ph2PC≡CPPh2反应, 生成硅杂环丙烯L(Cl)Si(η2-C2)(H)(PPh2) (4)、L(Cl)Si(η2-C2)(Ph)(PPh2) (5)、L(Cl)Si(η2-C2)(PPh2)2 (6). 1先后与Ph2PLi和MesLi进行基团交换反应, 得到膦基硅宾L(Ph2P)Si (2)和芳基硅宾L(Mes)Si (3, Mes = 2,4,6-Me3C6H2). 2和3分别与Ph2PC≡CPPh2反应, 生成硅杂环丙烯L(Ph2P)Si(η2-C2)(PPh2)2 (7)和L(Mes)Si(η2-C2)(PPh2)2 (8). 化合物4-8是一类含膦取代基的Si(η2-C2)-三元环化合物, 显示2个 π电子的Hückel芳香性的稳定结构, 是含硅杂环中张力最强的分子之一.

关键词： 硅宾; 官能基炔烃; 硅杂环丙烯; [1+2]-氧化环加成反应; X-射线单晶结构

本文引用格式

陈艺林 , 岳佳怡 , 林依鸣 , 刘兵妮 , 戴闻 , 朱红平 . 硅杂环丙烯的合成和表征[J]. 有机化学, 0 : 1 . DOI: 10.6023/cjoc202506023

Abstract

The chlorosilylene L(Cl)Si (1, L = PhC(NtBu)2) was synthesized. Compound 1 reacted with HC≡CPPh2, PhC≡CPPh2, Ph2PC≡CPPh2, producing silacyclopropenes L(Cl)Si(η²-C2)(H)(PPh2) (4), L(Cl)Si(η²-C2)(Ph)(PPh2) (5), and L(Cl)Si(η²-C2)(PPh2)2 (6), respectively. Metathesis reactions using 1 with the respective Ph2PLi and MesLi were further carried out, yielding phosphanyl and aryl silylenes L(Ph2P)Si (2) and L(Mes)Si (3, Mes = 2,4,6-Me3C6H2). Subsequently, the reactions of either 2 or 3 were able to occur with Ph2PC≡CPPh2, affording silacyclopropenes L(Ph2P)]Si(η²-C2)(PPh2)2 (7) and L(Mes)Si(η²-C2)(PPh2)2 (8), respectively. Compounds 4-8 are the type of the Si(η2-C2) three-membered ring compounds all containing the phosphanyl substituent, featuring the stable structure with 2 π electrons of the Hückel aromaticity. These compounds are considered as one of the most ring-strained molecules among the Si-containing heterocycles.

Key words： Silylene; Functionalized alkyne; Silacyclopropene; [1+2]-Oxidative cycloaddition; X-ray crystal structure

参考文献

[1] Volpin M. E.; Koreshkov Y. D.; Dulova V. G.; Kursanov D. N.Izv. Akad. Nauk. SSSR. Otd. Khim. Nauk. 1961, 1355-1358.
[2] Volpin M. E.; Koreshkov Y. D.; Dulova V. G.; Kursanov D. N.Tetrahedron 1962, 18, 107-122.
[3] (a) Johnson, F.; Gohlke, R. S.; Nasutavicus, W. A.J. Organomet. Chem. 1965, 3, 233-244.
(b) West, R.; Bailey, R. E. J. Am Chem. Soc. 1963, 85, 2871-2872.
[4] Conlin R. T.; Gaspar, P. P. J. Am. Chem. Soc.1976, 98, 3715-3716.
[5] Seyferth D.; Annarelli D. C.; Vick, S. C. J. Am. Chem. Soc.1976, 98, 6382-6384.
[6] Hirotsu K.; Higuchi T.; Ishikawa M.; Sugisawa H.; Kumada M.J. Chem. Soc., Chem. Commun. 1982, 726-727.
[7] (a) Baus J. A.; Laskowski N.; Tacke, R. Eur. J. Inorg. Chem. 2016,5182-5184.
(b) Ishikawa, M.; Naka, A.; Ohshita,J .Asian J. Org. Chem. 2015, 4, 1192-1209.
[8] So C.-W.; Roesky H. W.; Magull J.; Oswald, R. B. Angew. Chem. Int. Ed.2006, 45, 3948-3950.
[9] (a) Azhakar R.; Ghadwal R. S.; Roesky H. W.; Wolf H.; Stalke D. Organometallics2012, 31, 4588-4592.
(b) Zhao, Y.; Chen, Z.; Li, L.; Liu, C.; Zhu, H. Chin. J. Org. Chem. 2023, 43, 3590-3597.,766-775.)
[10] Cabeza J. A.; García-Álvarez P.; González-Álvarez L. Chem. Commun.2017, 53, 10275-10278.
[11] (a) Busacca C. A.; Lorenz J. C.; Nelu Grinberg, N. H. Organ. Lett.2005, 7, 4227-4280.
(b) Huang, Y.; Wang, X.; Li, Y.; Yang, M.-C.; Su, M.-D.; Zhu, H. Chem. Commun. 2019, 55, 1494-1497.
(c) Huang, Y.; Jiang, W.; Xi, X.; Li, Y.; Wang, X.; Yang, M.-C.; Zhang, Z.-F.; Su, M.-D.; Zhu, H. Eur. J. Inorg. Chem. 2020, 3496–3506.
[12] Xi X.; Zhang G.; Li J.; Huang Y.; Jiang W.; Wu P.; Zhu, H. Chin. J. Org. Chem.2021, 41, 766-775.(in Chinese)
(席鑫, 张公平, 李建成, 黄艳婷, 蒋文军, 吴鹏, 朱红平. 有机化学, 2021,41,766-775.)
[13] (a) Yu, J.; Kher, G.; Constantin C. G.; Erker, G.Inorg. Chem. 2013, 52, 11661-11668.
(b) Chen, Y. 博士毕业论文, 2022.
[14] Azhakar R.; Roesky H. W.; Wolf H.; Stalke, D. Z. Anorg. Allg. Chem.2013, 639, 934-938.
[15] Ishida S.; Iwamoto T.; Kira M. Heteroat. Chem.2011, 22, 432-437.
[16] Yao S.; Wüllen C.; Sun, X.-Y. Driess, M. Angew. Chem. Int. Ed.2008, 47, 3250-3253.
[17] Lips F.; Mansikkamäki A.; Fettinger J. C.; Tuononen H. M.; Power P. P. Organometallics2014, 33, 6253-6258.
[18] Protchenko A. V.; Blake M. P.; Schwarz A. D.; Jones C.; Mountford P.; Aldrige S.Organometallics 2015, 34, 2126-2129.
[19] Yao S.; Xiong Y.; van Wüllen C.; Driess M. Organometallics2009, 28, 1610-1612.
[20] Ohshita J.; Honda N.; Nada K.; Iida T.; Mihara T.; Matsuo Y.; Kunai A.; Naka A.; Ishikawa M.Organometallics 2003, 22, 2436-2441.
[21] Wang Z.; Zhang J.; Li J.; Cui, C. J. Am. Chem. Soc.2016, 138, 10421-10424.
[22] Jiang P.; Trieber D.; Gaspar P. P. Organometallics2003, 22, 2233-2239.
[23] Tsutsui S.; Tanaka H.; Kwon E.; Matsumoto S.; Sakamoto K. Organometallics2004, 23, 5659-5661.
[24] Ando W.; Shiba T.; Hidaka T.; Morihashi K.; Kikuchi, O. J. Am. Chem. Soc.1997, 119, 3629-3630.
[25] Kunai A.; Matsuo Y.; Ohshita J.; Ishikawa M.; Aso Y.; Otsubo T.; Ogura F.Organometallics 1995, 14, 1204-1212.
[26] Ostendorf D.; Saak W.; Weidenbruch M. Organometallics2000, 19, 4938-4940.
[27] (a) Ding S.; Li J.; Liu R.; Fu G.; Zhu H.; Liu W.; Ye, Q. ACS. Omega 2017, 2,2405-2414.
(b) Chen, Y.; Jiang, W.; Li, B.; Fu, G.; Chen, S.; Zhu, H.Dalton Trans. 2019, 48, 9152-9160.
[28] Zhao Y; Truhlar, D. G. Theo. Chem. Acc.2008, 120, 215-241.
[29] (a) Krishnan R.; Binkley J. S.; Seeger R.; Pople, J. A. J. Chem. Phys.1980, 72, 650-654.
(b) Frisch, M. J.; Pople, J. A.; Binkley, J. S. J. Chem. Phys. 1984, 80, 3265-3269.
[30] (a) Reed, A. E.; Weinhold, F. J. Chem. Phys. 1983, 78, 4066-4073.
(b) Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735-746.
(c) Reed, A. E.; Weinhold, F. J. Chem. Phys. 1985, 83, 1736-1740.
(d) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899-926.
(e) Carpenter, J. E.; Weinhold, F. J. Mol. Struct. (Theochem) 1988, 46, 41-62.
(f) Foster, J. P.; Weinhold, F. J. Am. Chem. Soc. 1980, 102, 7211-7218.
[31] 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, J. M.; 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, 2009.
[32] (a) Lu T.; Chen, F. W. J. Comput. Chem.2012, 33, 580-592.
(b) Zhang, J.; Lu, T. Phys. Chem. Chem. Phys. 2021, 23, 20323-20328.
Options
文章导航

/

〈 〉