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

doi:10.7503/cjcu20140252

Abstract

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

CLC Number:

O626

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2014, 35(11): 2341.

Figures/Tables 5

References 22

[1]	West R., Comprehensive Organometallic Chemistry, Vol.9, Pergamon, Oxford, 1983, 365—397
[2]	Schubert U., Angew. Chem. Int. Ed. Eng., 1994, 33, 419—421
[3]	Sharma H. K., Pannell K. H., Chem. Rev., 1995, 95, 1351—1374
[4]	Suginome M., Ito Y., J. Chem. Soc.,Dalton Trans., 1998, 1925—1934
[5]	Sun H., Zhang Z., Pan Y., Yang J., Zhou X., Inorg. Chem., 2003, 42, 4076—4081
[6]	Sun H., Pan Y., Huang X., Guo Z., Zhang Z., Zhang H., Li J., Wang F., Organometallics,2006, 25, 133—139
[7]	Zhang Z., Gu J., Zhang C., Sun H., Organometallics,2008, 27(12), 2149—2151
[8]	Sun H., Chen Z., Zhou Z., Inorg. Chim. Acta,2003, 355, 404—407
[9]	Sun H. L., Zhang H. L., Ma Y. X., Chem. J. Chinese Universities,2006, 27(12), 2097—2100
	(孙怀林, 张会利, 马玉新. 高等学校化学学报,2006, 27(12), 2097—2100)
[10]	Sun H. L., Xu S. S., Zhou X. Z., Chin. J. Org. Chem., 2003, 23, 996—1000
	(孙怀林, 徐善生, 周秀中. 有机化学, 2003, 23, 996—1000)
[11]	Liu Q. H., Sun H. L., Chem. J. Chinese Universities,2011, 32(7), 1537—1540
	(刘秋华, 孙怀林. 高等学校化学学报,2011, 32(7), 1537—1540)
[12]	Ishikawa M., Nakagawa K. I., Kumada M., J. Organomet. Chem., 1979, 178, 105—118
[13]	Oka K., Nakao R., J. Organomet. Chem., 1990, 390, 7—18
[14]	Detty M. R., Murray B. J., Smith D. L., Zumbulyadis N., J. Am. Chem. Soc., 1983, 105, 875—882
[15]	Baines K. M., Brook A. G., Ford R. R., Lickiss P. D., Saxena A. K., Chatterton W. J., Sawyer J. F., Behnam B. A., Organometallics,1989, 8, 693—709
[16]	Sanganee M. J., Steel P. G., Whelligan D. K., J. Org. Chem., 2003, 68, 3337—3339
[17]	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 J. 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 B.01, Gaussian Inc., Wallingford CT, 2009
[18]	Fukui K., Acc. Chem. Res., 1981, 14, 363—368
[19]	Becke A. D., J. Chem. Phys., 1993, 98, 5648—5652
[20]	Stephens P. J., Devlin F. J., Chabalowski C. F., Frisch M. J., J. Phys. Chem., 1994, 98, 11623—11627
[21]	Hay P. J., Wadt W. R., J. Chem. Phys., 1985, 82, 270—283
[22]	Ehlers A. W., Gobbi A., Höllwarth A., Böhme M., Dapprich S., Jonas V., Köhler K. F., Stegmann R., Veldkamp A., Frenking G., Chem. Phys. Lett., 1993, 208, 111—114

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)

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

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 5

References 22

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	ZHANG Yongpo, ZHANG Yang, SUN Huailin. Stereo Selective Synthesis and Absolute Configuration Determination of (2E,4S)-4-(t-butoxycarbonylamino)-5-[(3S)-2'-oxo-3'-pyrrolidinyl]-2-pentenoic Acid Ethyl Ester^† [J]. Chem. J. Chinese Universities, 2014, 35(2): 292.
[2]	LIU Hao, XU Fen, SUN Li-Xian, CAO Zhong, ZHOU Huai-Ying. Preparation and Hydrogen Generation for Al-LiBH₄ Composite Materials [J]. Chem. J. Chinese Universities, 2013, 34(8): 1953.
[3]	SHAO Chun-Guang, ZHUO Ran-Ran, LI Qian, CAO Wei, ZHANG Yang, ZHANG Rui-Jing, LIU Cheng-Gang, SHEN Chang-Yu. Relationship Between Crystal Orientation and Stress-induced Crystalline Melting of Syndiotactic Polypropylene Under Uniaxial Deformation via in situ Wide-angle X-ray Scattering [J]. Chem. J. Chinese Universities, 2013, 34(2): 485.
[4]	ZHOU Jing, LI Liang, HUANG Feng-Xian, SHEN Hong-Zhi, YANG Hang, ZHOU Qiang, WANG Wen-Quan, XU Da-Peng. In-situ Raman Spectra and X-ray Diffraction Study on Pressure-induced Phase Transition in Columbite ZnNb₂O₆ [J]. Chem. J. Chinese Universities, 2013, 34(10): 2383.
[5]	LIU Qiu-Hua, SUN Huai-Lin. Synthesis, Structure and Si—Si Bond Stability of η6-[Tris(trimethylsilyl)phenylsilane]tricarbonylmolybdenum Complexes [J]. Chem. J. Chinese Universities, 2011, 32(7): 1537.
[6]	GUO Xing-Yuan, DING Zhan-Hui, ZHAO Xu-Dong, QIU Li-Xia, XUE Yan-Feng, .... Influence of Excitation Intensities on Photoluminescence of ZnO(Wurtzite) Whiskers at Room Temperature [J]. Chem. J. Chinese Universities, 2010, 31(2): 243.
[7]	ZHENG Yi-Fan, LIU Hua-Zhang, LI Xiao-Nian. In situ X-ray Diffraction Investigation on Reduction Process of Ammonia-synthesis Fused-iron Catalysts and the Formation Mechanism of Its Active Phase [J]. Chem. J. Chinese Universities, 2009, 30(6): 1177.
[8]	SHI Shu-Yun^1,2, ZHAO Yu², ZHANG Yu-Ping¹, HUANG Ke-Long¹, LIU Su-Qin¹. Separatian and Identification of Constituents from Ligularia atroviolacea* [J]. Chem. J. Chinese Universities, 2008, 29(5): 941.
[9]	JIANG Fan1,2, WU Yun-Dong1,2*. Theoretical Studies on Shortest α-Helix [J]. Chem. J. Chinese Universities, 2008, 29(12): 2371.
[10]	SUN Feng-Mei, SHI De-Qing, TIAN Man-Man, TAN Xiao-Song. Synthesis and Biological Activities of 2-oxo-2-[1-(3-pyridylmethylamino)-1'-aryl]methyl-4-aryl-5,5-dimethyl-1,3,2-dioxaphosphinane [J]. Chem. J. Chinese Universities, 2006, 27(11): 2092.
[11]	SUN Huai-Lin, ZHANG Hui-Li, MA Yu-Xi . Synthesis and Thermal Rearrangement of 1,2-Di(p-tolyl)-1,2-dimethyldisilanylene Bridged Bis(cyclopentadienyl)tetracarbonyldiiron [J]. Chem. J. Chinese Universities, 2006, 27(11): 2097.
[12]	GUO Xing-Yuan¹, YU Ying-Ning², XU Da-Peng¹, DING Zhan-Hui¹, SU Wen-Hui^1,3,4. Growth of ZnO(Wurtzite) Whiskers Using the Floating Zone Method at High Oxygen Pressure [J]. Chem. J. Chinese Universities, 2006, 27(10): 1811.
[13]	LIU Lei-Jing, GENG Jian-Xin, ZHOU Yun-Chun, YIN Li, LI Gao, ZHOU En-Le, Jacky Lam Wing Yip, Tang Ben-Zhong. Crystal Structure of 5[(4'-Heptoxy-biphenylyl-4-yl)oxy]carbonyl-1-pentyne [J]. Chem. J. Chinese Universities, 2005, 26(7): 1366.
[14]	ZHANG Sheng-Mao, ZHANG Zhi-Jun, DANG Hong-Xin, LIU Wei-Min, XUE Qun-Ji . Preparation and Characterization of Orderly Alternating TiO₂/CTAB Multilayer Film [J]. Chem. J. Chinese Universities, 2003, 24(6): 1136.
[15]	LU Yi, ZHU Zhen-Ping, WU Wei-Ze, LIU Zhen-Yu . Preparation of Carbon Nanotubes by Catalysis-assisted Detonation [J]. Chem. J. Chinese Universities, 2003, 24(6): 1063.