η6-[三(三甲基硅基)苯基硅烷]三羰基铬类化合物的合成及其分子内硅硅键与金属铬之间相互作用的理论研究

doi:10.7503/cjcu20140252

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (11): 2341.doi: 10.7503/cjcu20140252

η⁶-[三(三甲基硅基)苯基硅烷]三羰基铬类化合物的合成及其分子内硅硅键与金属铬之间相互作用的理论研究

吕浩挺, 刘婷婷, 张明涛, 刘洁, 孙怀林()

南开大学化学系, 化学与工程协同创新中心, 天津 300071

收稿日期:2014-03-24 出版日期:2014-11-10 发布日期:2014-10-15
作者简介:联系人简介: 孙怀林, 男, 博士, 教授, 博士生导师, 主要从事有机硅化学与过渡金属有机化学研究. E-mail:sunhl@nankai.edu.cn
基金资助:
国家自然科学基金(批准号: 20834002)、天津市自然科学基金(批准号: 08JCZDJC21600)和高等学校博士学科点专项科研基金(批准号: 20090031110012)资助

Synthesis of η⁶-[Tris(trimethylsilyl)phenylsilane]tricarbonylchromium Complexes and Theoretical Studies on the Possible Interaction of Intermolecular Si—Si Bonds and Chromium Centers^†

LÜ Haoting, LIU Tingting, ZHANG Mingtao, LIU Jie, SUN Huailin^*()

Department of Chemistry and Collaborative Innovation Center of Chemical Science and Engineering,Nankai University, Tianjin 300071, China

Received:2014-03-24 Online:2014-11-10 Published:2014-10-15
Contact: SUN Huailin E-mail:sunhl@nankai.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.20834002), the Natural Science Foundation of Tianjin, China(No.08JCZDJC21600) and the Research Fund for the Doctoral Program of Higher Education, China(No.20090031110012)

摘要/Abstract

摘要：

采用三(三甲基硅基)苯基硅烷p-R(Me₃Si)₃SiC₆H₄与六羰基铬在加热条件下反应, 制得了相应的η⁶-[三(三甲基硅基)苯基硅烷]三羰基铬化合物{η⁶-[(Me₃Si)₃SiC₆H₄R]Cr(CO)₃(R=H, p-Me, p-MeO)}. 利用核磁共振波谱、红外光谱和元素分析等手段对产物进行了表征, 并利用单晶X射线衍射法测定了化合物η⁶-[(Me₃Si)₃SiC₆H₄R]Cr(CO)₃(R=H) 的分子结构. 在此基础上, 对其分子内硅硅键与金属铬之间可能的相互作用进行了考察, 发现在加热条件下硅硅键不能被分子内过渡金属活化. 利用密度泛函理论(DFT)对预测的硅硅键活化过程进行了计算, 发现反应可能的中间体、过渡态及最终产物均具有较高能量, 导致反应在动力学和热力学上均不可行. 这一结果表明, 分子内硅硅键被过渡金属活化的现象在η⁶-苯基金属化合物体系中难以发生.

关键词: 硅硅键, 羰基铬, η⁶-苯基络合物, X射线衍射, 密度泛函理论计算

Abstract:

Intramolecular Si—Si bond activation by transition metals has been widely found in transition metal complexes with polysilanyl substituted η⁴- and η⁵-ligands, but such activation in η⁶-phenyl complexes keeps unknown. In this study, η⁶-[tris(trimethylsilyl)phenylsilane]tricarbonyl chromium complexes, η⁶-[(SiMe₃)₃SiC₆H₄R]Cr(CO)₃(R=H, Me and MeO), were synthesized by reaction of tris(trimethylsilyl)phenylsilane, p-R(Me₃Si)₃SiC₆H₄ with hexacarbonylchromium in diethylene glycol dimethyl ether. The products were characterized by ¹H NMR, ¹³C NMR, IR spectra and elemental analyses. The molecular structure of η⁶-[(SiMe₃)₃SiC₆H₄R]Cr(CO)₃(R=H) was determined by the X-ray diffraction method. The possibility of the Si—Si bond activation by the intramolecular chromium center was examined experimentally. The results showed that the Si—Si bonds in the complexes were stable under thermal conditions. Density functional theory(DFT) calculation of possible Si—Si bond activation processes indicated that all the reaction interme-diates and transition states had such high energies that the Si—Si bonds were unable to be activated by the intramolecular chromium center. These results demonstrated that Si—Si bond activation should be difficult to take place in polysilanyl substituted η⁶-phenyl transition metal systems.

Key words: Silicon-silicon bond, Carbonylchromium, η⁶-Phenyl complex, X-Ray diffraction, Density functional theory(DFT) calculation

中图分类号:

O626

TrendMD:

吕浩挺, 刘婷婷, 张明涛, 刘洁, 孙怀林. η⁶-[三(三甲基硅基)苯基硅烷]三羰基铬类化合物的合成及其分子内硅硅键与金属铬之间相互作用的理论研究. 高等学校化学学报, 2014, 35(11): 2341.

LÜ Haoting, LIU Tingting, ZHANG Mingtao, LIU Jie, SUN Huailin. Synthesis of η⁶-[Tris(trimethylsilyl)phenylsilane]tricarbonylchromium Complexes and Theoretical Studies on the Possible Interaction of Intermolecular Si—Si Bonds and Chromium Centers^†. Chem. J. Chinese Universities, 2014, 35(11): 2341.

图/表 5

参考文献 22

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Empirical formula	C₁₈H₃₂CrO₃Si₄	Temperature/K	113(2)
Formula mass	460.8	F(000)	976
Crystal system	Monoclinic	θ range for data collection(°)	2.28—27.87
Space group	P2₁/c	Limiting index	-18≤h≤17, -10≤k≤10, -21≤l≤17
a/nm	1.5594(3)	Reflections collected/unique	13956/4371(R_int=0.0297)
b/nm	0.91257(18)	Completeness to θ=25.02°(%)	99.4
c/nm	1.8131(4)	Absorption correction	Semi-empirical from equivalents
α/(°)	90	Max. and min. transmission	0.9124 and 0.8894
β/(°)	105.48(3)	Refinement method	Full-matrix least-squares onF²
γ/(°)	90	Data/restraints/parameters	4371/0/244
Volume/nm³	2.4867(9)	Goodness-of-fit on F²	1.158
Z	4	Final R indices [I>2σ(I)]	R₁=0.0263, wR₂=0.0731
Calculated density/(g·cm^-3)	1.231	R index(all data)	R₁=0.0303, wR₂=0.0829
Absorption coefficient/mm^-1	0.667	Largest diff. peak and hole/(e·nm^-3)	331 and -390

Empirical formula	C₁₈H₃₂CrO₃Si₄	Temperature/K	113(2)
Formula mass	460.8	F(000)	976
Crystal system	Monoclinic	θ range for data collection(°)	2.28—27.87
Space group	P2₁/c	Limiting index	-18≤h≤17, -10≤k≤10, -21≤l≤17
a/nm	1.5594(3)	Reflections collected/unique	13956/4371(R_int=0.0297)
b/nm	0.91257(18)	Completeness to θ=25.02°(%)	99.4
c/nm	1.8131(4)	Absorption correction	Semi-empirical from equivalents
α/(°)	90	Max. and min. transmission	0.9124 and 0.8894
β/(°)	105.48(3)	Refinement method	Full-matrix least-squares onF²
γ/(°)	90	Data/restraints/parameters	4371/0/244
Volume/nm³	2.4867(9)	Goodness-of-fit on F²	1.158
Z	4	Final R indices [I>2σ(I)]	R₁=0.0263, wR₂=0.0731
Calculated density/(g·cm^-3)	1.231	R index(all data)	R₁=0.0303, wR₂=0.0829
Absorption coefficient/mm^-1	0.667	Largest diff. peak and hole/(e·nm^-3)	331 and -390

Cr1—C9	0.22552(17)	Cr1—C8	0.22050(18)
Cr1—C7	0.2208(2)	Cr1—C6	0.22124(19)
Cr1—C5	0.22177(19)	Cr1—C4	0.22054(18)
Si1—C9	0.19087(17)	Si1—Si2	0.23555(7)
Si1—Si3	0.23545(8)	Si1—Si4	0.23564(10)
C1—Cr1—C2	87.63(9)	C1—Cr1—C3	86.80(8)
C3—Cr1—C2	89.26(9)	C9—Si1—Si3	111.89(6)
C9—Si1—Si2	111.93(6)	Si3—Si1—Si2	111.09(2)

Cr1—C9	0.22552(17)	Cr1—C8	0.22050(18)
Cr1—C7	0.2208(2)	Cr1—C6	0.22124(19)
Cr1—C5	0.22177(19)	Cr1—C4	0.22054(18)
Si1—C9	0.19087(17)	Si1—Si2	0.23555(7)
Si1—Si3	0.23545(8)	Si1—Si4	0.23564(10)
C1—Cr1—C2	87.63(9)	C1—Cr1—C3	86.80(8)
C3—Cr1—C2	89.26(9)	C9—Si1—Si3	111.89(6)
C9—Si1—Si2	111.93(6)	Si3—Si1—Si2	111.09(2)

η⁶-[三(三甲基硅基)苯基硅烷]三羰基铬类化合物的合成及其分子内硅硅键与金属铬之间相互作用的理论研究

Synthesis of η⁶-[Tris(trimethylsilyl)phenylsilane]tricarbonylchromium Complexes and Theoretical Studies on the Possible Interaction of Intermolecular Si—Si Bonds and Chromium Centers^†

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