芳基铜(I)与烷基硅胺的反应: 无限链芳基铜(I)、多核硅胺铜(I)及纳米粒子铜(0)的合成和表征

doi:10.6023/cjoc202501007

有机化学 ›› 2025, Vol. 45 ›› Issue (8): 2848-2853.DOI: 10.6023/cjoc202501007 上一篇下一篇

研究论文

芳基铜(I)与烷基硅胺的反应: 无限链芳基铜(I)、多核硅胺铜(I)及纳米粒子铜(0)的合成和表征

林依鸣^a^,^†, 岳佳怡^a^,^†, 张春燕^a^,^†, 陈艺林^b^,^*(), 朱红平^a^,^*()

^a 厦门大学化学化工学院固体表面物理化学国家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:2025-01-12 修回日期:2025-03-18 发布日期:2025-04-24
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)

Reactions of Copper(I) Aryls and Siladiamine: Synthesis and Characterization of (CuMes)_n, Multinuclear Copper(I) Siladiamide and Copper(0) Nanoparticles

Yiming Lin^a, Jiayi Yue^a, Chunyan Zhang^a, Yilin Chen^b^,^*(), Hongping Zhu^a^,^*()

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

Received:2025-01-12 Revised:2025-03-18 Published:2025-04-24
Contact: *E-mail:chenyl@natachem.com;hpzhu@xmu.edu.cn
About author:
†These 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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摘要/Abstract

研究了芳基铜(I)和烷基硅胺的反应, 合成了无限链芳基铜(I)、多核硅胺铜(I)化合物以及纳米粒子铜金属. 2,4,6-三甲基苯基铜(I) [(CuMes)₄]在二甲基硅二叔丁胺[Me₂Si(NH^tBu)₂]的存在下于氘苯溶剂中90 ℃下放置12 h, 转化成一维无限链状结构的(CuMes)_n (1). 该体系在反应时间延长至22 h时产生面心立方相、平均粒径3.25 nm的铜金属纳米粒子. 2 equiv.五氟苯基铜(I) [(CuC₆F₅)₂•dioxane]与Me₂Si(NH^tBu)₂在苯溶剂中80 ℃下反应8 h, 生成四核硅胺铜(I)化合物Cu₂[N(^tBu)SiMe₂]₂[NH(^tBu)SiMe₂]₂(CuC₆F₅)₂ (2). 测定了化合物1和2的单晶衍射结构, 测试了铜金属纳米粒子的X射线粉末衍射(XRD)和高能透射电子显微镜(TEM)谱; 研究了(CuMes)₄和Me₂Si(NH^tBu)₂在氘苯中的反应动力学, 证明了铜金属纳米粒子的关键成因, 即(CuMes)_{4 or}_n或类硅胺铜(I)化合物发生了依赖于温度和反应时间的自氧化还原反应. 首次实验证实了一维无限链状芳基铜(I)结构的存在.

关键词: 芳基铜(I), 烷基硅胺, 一维无限链状结构, 多核硅胺铜(I), 铜金属纳米粒子, 反应动力学

Abstract Reactions of copper(I) aryls and siladiamine were studied, and infinite one-dimensional linear arylcopper(I), multinuclear copper(I) siladiamide and copper(0) nanoparticles (NPs) were resulted. The reaction of (CuMes)₄ in the presence of Me₂Si(NH^tBu)₂ in C₆D₆ at 90 ℃ yielded (CuMes)_n (1) after 12 h. When this reaction was treated by prolonging the time to 22 h, Cu(0) NPs were transformed and tested to be of the face-centered cubic phase with averaged diameter of 3.25 nm. The reaction of Me₂Si(NH^tBu)₂ and two equivalent (CuC₆F₅)₂•dioxane in benzene at 80 ℃ gave tetranuclear copper(I) siladiamide Cu₂[N(^tBu)SiMe₂]₂[NH(^tBu)SiMe₂]₂(CuC₆F₅)₂ (2) within 8 h. Compounds 1 and 2 have been determined by X-ray crystallography. The Cu(0) NPs were characterized by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). The kinetic reaction of (MesCu)₄ and Me₂Si(NH^tBu)₂ in C₆D₆ at 90 ℃ for 12 d was studied by ¹H NMR spectroscopy, which proved formation of the Cu(0) NPs by temperature and time-dependent self-redox of the copper(I) siladiamide formed along with (CuMes)_{4 or}_n. The structure of an infinite one-dimensional linear arylcopper(I) by 1 was testified, for the first time, to exist in experiment.

Key words: arylcopper(I), siladiamine, infinite one-dimensional linear structure, multinuclear copper(I) siladiamide, copper(0) nanoparticles, kinetic reaction

引用此文

林依鸣, 岳佳怡, 张春燕, 陈艺林, 朱红平. 芳基铜(I)与烷基硅胺的反应: 无限链芳基铜(I)、多核硅胺铜(I)及纳米粒子铜(0)的合成和表征[J]. 有机化学, 2025, 45(8): 2848-2853.

Yiming Lin, Jiayi Yue, Chunyan Zhang, Yilin Chen, Hongping Zhu. Reactions of Copper(I) Aryls and Siladiamine: Synthesis and Characterization of (CuMes)_n, Multinuclear Copper(I) Siladiamide and Copper(0) Nanoparticles[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2848-2853.

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图/表 7

图式1. 化合物1的合成

Scheme 1. Synthesis of compound 1

图式2. 化合物2的合成

Scheme 2. Synthesis of compound 2

图1. 化合物1的X射线晶体结构图

Figure 1. X ray crystal structure of compound 1 A is for the determined fragment, B is a view of the packed molecule along the axis, C is a view of the packed molecule along the c axis, and D is space-filling drawing. Hydrogen atoms are omitted for clarity. Selected bond lengths (nm) and angles (°): Cu(1)—C(1) 0.1994(6), Cu(1)—C(11) 0.1983(6), Cu(2)—C(1) 0.2005(6), Cu(3)—C(11) 0.1988(6), Cu(1)…Cu(2) 0.24579(8), Cu(1)…Cu(3) 0.24547(8); C(1)—Cu(1)—C(11) 162.5(3), Cu(1)—C(1)—Cu(2) 75.8(2), Cu(1)—C(11)—Cu(3) 76.4(2), C(1)—Cu(2)—C(1A) 180.0(1), C(11)—Cu(3)—C(11B) 180.0(2), Cu(2)…Cu(3)…Cu(1) 124.91(3), Cu(1)…Cu(2)…Cu(1A) 180.0(4). Symmetry code: －x＋1, －y＋1, －z (for A), －x, －y＋1, －z (for B).

图2. 化合物2的晶体结构

Figure 2. X-ray crystal structure of compound 2 Hydrogen atoms except for the NH one are omitted for clarity. Selected bond lengths (nm) and angles (°): Cu(1)—N(1) 0.1945(2), Cu(1)—N(2) 0.1908(2), Cu(2)—N(2) 0.1942(2), Cu(2)—C(11)0.1899(3), Si(1)—N(2) 0.1737(2), Si(1)—N(1A) 0.1826(2), Cu(1)…Cu(2) 0.26819(4), Cu(1)…Cu(1A) 0.27482(6); C(11)—Cu(2)—N(2) 176.74(11), N(2)—Cu(1)—N(1) 175.43(9), C(1)—Si(1)—C(2) 107.49(13), N(2)—Si(1)—N(1A) 106.80(10). Symmetry code: －x＋1, －y＋1, －z (for A).

图3. Cu纳米粒子的XRD谱图

Figure 3. XRD pattern of the Cu NPs The upper one is for the product and the down one is for the standard sample (JCPDS 01-089-2838)

图4. Cu纳米粒子的TEM图谱

Figure 4. TEM images of the Cu NPs

图5. (MesCu)4和Me2Si(NHtBu)2在C6D6中90 ℃下1H NMR谱跟踪反应研究

Figure 5. 1H NMR spectroscopic study on reaction of (MesCu)4 and Me2Si(NHtBu)2 in C6D6 at 90 ℃ for 12 d I and II depict the proton resonance changes of the respective methyl (δ 1.8~3.2) and aryl (δ 6.5~7.2) group of (MesCu)4 with the reaction times.

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芳基铜(I)与烷基硅胺的反应: 无限链芳基铜(I)、多核硅胺铜(I)及纳米粒子铜(0)的合成和表征

Reactions of Copper(I) Aryls and Siladiamine: Synthesis and Characterization of (CuMes)_n, Multinuclear Copper(I) Siladiamide and Copper(0) Nanoparticles

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