硅杂环丙烯的合成和表征

doi:10.6023/cjoc202506023

摘要/Abstract

合成了氯代硅宾化合物L(Cl)Si (1, L=PhC(Nt-Bu)₂). 1分别与HC≡CPPh₂、PhC≡CPPh₂和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

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

引用此文

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, 2026, 46(1): 128-134.

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

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图/表 13

图式1. 化合物1的合成

Scheme 1. Synthesis of compound 1

图式2. 化合物2和3的合成

Scheme 2. Synthesis of compounds 2 and 3

图式3. 硅杂环丙烯4~8的合成

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

表1. 化合物4～6中Si(η2-C2)环的13C和29Si以及PPh2 基团31P 的NMR 数据

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

图1. 化合物4中Si(η2-C2)-芳香环的特征NMR (1H, 13C, 29Si和31P)谱

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

图2. 化合物4的50%热椭圆球体晶体结构图

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

图3. 化合物6的50%热椭圆球体晶体结构图

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

图4. 化合物7的50%热椭圆球体晶体结构图

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

图5. 化合物8的30%热椭圆球体晶体结构图

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)

表2. 化合物4和6~8中Si(η2-C2)环的重要键长(nm)和键角(°)

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

图式4. 硅宾与取代炔烃反应生成硅杂环丙烯的可能作用机理

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

图6. DFT计算的L(Cl)Si和PPh2C≡CH生成L(Cl)Si(η2-C2)- (H)(PPh2)的反应中三个化合物分子的电荷密度分布状态图

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

表3. NBO分析法计算的不同取代基炔烃分子中C≡C键C原子的电荷分布数值

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

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