Synthesis and Characterization of Silacyclopropenes

doi:10.6023/cjoc202506023

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (1): 128-134.DOI: 10.6023/cjoc202506023 Previous Articles Next Articles

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硅杂环丙烯的合成和表征

陈艺林^b^,^*(), 岳佳怡^a^,^†, 林依鸣^a^,^†, 刘兵妮^a, 戴闻^a, 朱红平^a^,^*()

^a 厦门大学化学化工学院表界面化学全国重点实验室福建厦门 361005
^b 江苏南大光电股份有限公司江苏苏州 210046

收稿日期:2025-06-17 修回日期:2025-08-04 发布日期:2025-09-23
通讯作者: 陈艺林, 朱红平
作者简介:
^† 共同第一作者
基金资助:
国家自然科学基金(21972112); 福建省产学研(2021H6002)

Synthesis and Characterization of Silacyclopropenes

Chen Yilin^b^,^*(), Yue Jiayi^a, Lin Yiming^a, Liu Bingni^a, Dai Wen^a, Zhu Hongping^a^,^*()

^a State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005
^b Jiangsu Nata Opto-electronic Material Co., Ltd., Soochow, Jiangsu 210046

Received:2025-06-17 Revised:2025-08-04 Published:2025-09-23
Contact: Chen Yilin, Zhu Hongping
About author:
^† The authors contributed equally to this work
Supported by:
National Natural Science Foundation of China(21972112); Productive Research Program of Fujian Province(2021H6002)

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Abstract

The chlorosilylene L(Cl)Si (1, L=PhC(Nt-Bu)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 and 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

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Chen Yilin, Yue Jiayi, Lin Yiming, Liu Bingni, Dai Wen, Zhu Hongping. Synthesis and Characterization of Silacyclopropenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 128-134.

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Fig. & Tab. 13

Scheme 1. Synthesis of compound 1

Scheme 2. Synthesis of compounds 2 and 3

Scheme 3. Synthesis of silacyclopropenes 4~8

Compd.	SiC₂	SiC₂	PPh₂
4	－134.6	170.52, 194.60	－6.47
5	－139.58	174.38, 189.23	－12.33
6	－139.32	189.66	－7.41

Table 1. Key NMR data of the 13C and 29Si for the Si(η2-C2)- cycle and the 31P for the PPh2 group from compounds 4~6

Figure 1. Characterized NMR spectra (1H, 13C, 29Si, and 31P) for the aromatic Si(η2-C2)-cycle of compound 4

Figure 2. X-ray crystal structure of compound 4 with thermal ellipsoids at 50% probability

Figure 3. X-ray crystal structure of compound 6 with thermal ellipsoids at 50% probability

Figure 4. X-ray crystal structure of compound 7 with thermal ellipsoids at 50% probability

Figure 5. X-ray crystal structure of compound 8 with thermal ellipsoids at 30% probability

Comp.		C—C/nm	Si—C—C/(°)
4	0.1781(2) 0.1842(2)	0.1351(3)	65.76(10) 70.50(11)	43.74(8)
6	0.1788(3) 0.1830(3)	0.1371(5)	66.12(18) 69.40(20)	44.52(15)
7	0.1806(2) 0.1871(2)	0.1365(2)	65.71(7) 70.77(7)	43.52(5)
8	0.1806(2) 0.1880(2)	0.1361(2)	65.44(9) 71.27(9)	43.29(7)

Table 2. Important bond length (nm) and angle (°) for the Si(η2-C2)-cycle of compounds 4 and 6~8

Scheme 4. Proposed interaction mechanism of the silylene and substituted alkyne to silacyclopropene

Figure 6. Charge density distribution states for molecules of three compounds involved in reaction of L(Cl)Si and PPh2C≡CH to L(Cl)Si(η2-C2)(H)(PPh2) performed by DFT calculations

R¹	R²	C¹	C²
H	SiMe₃	－0.187	－0.487
H	OEt	－0.383	0.327
H	nBu	0.005	0.249
H	PPh₂	－0.113	－0.342
H	Ph	－0.192	－0.033
Et	CO₂Et	0.062	－0.151
Ph	SiMe₃	0.008	－0.451
Ph	Me	－0.078	0.025
Ph	Et	－0.074	0.012
Ph	Pr	－0.073	0.018
Ph	CO₂Et	0.040	－0.107
Ph	PPh₂	0.135	－0.359
PPh₂	SiHMe₂	－0.300	－0.407
PPh₂	SiHPh₂	－0.279	－0.418

Table 3. Charge distribution calculated for the C≡C carbon atoms of the substituted alkynes by the NBO analysis method

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硅杂环丙烯的合成和表征

Synthesis and Characterization of Silacyclopropenes

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