cis-[Ni(NCS)2tren]的镜面对称性破缺: 螯环的特殊手性构象

doi:10.3866/PKU.WHXB201112091

物理化学学报 >> 2012, Vol. 28 >> Issue (02): 257-264.doi: 10.3866/PKU.WHXB201112091

cis-[Ni(NCS)₂tren]的镜面对称性破缺: 螯环的特殊手性构象

刘成勇, 颜建新, 林以玑, 李丹, 方雪明, 章慧

厦门大学化学化工学院化学系, 固体表面物理化学国家重点实验室, 福建厦门 361005

收稿日期:2011-09-28 修回日期:2011-12-01 发布日期:2012-01-11
通讯作者: 章慧 E-mail:huizhang@xmu.edu.cn
基金资助:
国家自然科学基金(20773098, 20973136)资助项目

Mirror Symmetry Breaking of cis-[Ni(NCS)₂tren]: Special Chiral Conformations of Chelate Rings

LIU Cheng-Yong, YAN Jian-Xin, LIN Yi-Ji, LI Dan, FANG Xue-Ming, ZHANG Hui

State Key Laboratory of Physical Chemistry of Solid Surface, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China

Received:2011-09-28 Revised:2011-12-01 Published:2012-01-11
Contact: ZHANG Hui E-mail:huizhang@xmu.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (20773098, 20973136).

摘要/Abstract

摘要： 为了探究cis-[Ni(NCS)₂tren] [tren: 三(2-氨基乙基)胺]的手性来源, 本文采用单晶X射线衍射、溶液紫外-可见-近红外(UV-Vis-NIR)光谱、固体紫外圆二色(CD)光谱和粉末X射线衍射(XRD)等对cis-[Ni(NCS)₂tren]的一对手性晶体进行了表征. 研究结果表明: 该手性晶体由结晶过程中的镜面对称性破缺而形成; 三角架型配体tren 配位后的特殊手性构象(δδλ, λλδ)是cis-[Ni(NCS)₂tren]的主要手性来源. 络合物固体紫外CD谱所呈现的Cotton 效应可能来自其螯环手性构象以及手性金属中心对NCS-配体的π-π^*跃迁和荷移跃迁生色团的手性微扰. 对20批次合成产物进行固体CD检测的统计结果表明: 它们的对映体过量(ee)值在39%-100%之间.

关键词: 手性, 镜面对称性破缺, 螯环构象异构, 三(2-氨基乙基)胺, 固体CD光谱

Abstract: In order to explore the chiral origin of cis-[Ni(NCS)₂tren] [tren: tris(2-aminoethyl) amine], a pair of chiral crystals of cis-[Ni(NCS)₂tren] was characterized by X-ray single crystal structural analysis, solution UV-Vis-near infrared (NIR) spectroscopy, solid state UV-circular dichiroism (CD), and powder X-ray diffraction (XRD) spectra. The results indicated that the chiral crystals of cis-[Ni(NCS)₂tren] were obtained by mirror symmetry-breaking crystallization, and the special chiral ring conformations (δδλ, λλδ) of the coordinated tripod-type tren ligands are responsible for the chiral origin of cis-[Ni(NCS)₂tren]. The Cotton effects of Ni(II) complexes in the solid-state UV-CD spectra are presumably attributed to the π-π^* and charge-transfer chromophores of the NCS^- ligands by the chiral perturbation of the helical ring conformations and metal-centered chirality. According to the statistical results of solid-state CD spectra of cis-[Ni(NCS)₂tren] for twenty batch syntheses, their enantiomeric excess (ee) values are between 39% and 100%.

Key words: Chirality, Mirror symmetry breaking, Ring conformational isomerism, Tris(2-aminoethyl)amine, Solid state CD spectroscopy

MSC2000:

O641

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刘成勇, 颜建新, 林以玑, 李丹, 方雪明, 章慧. cis-[Ni(NCS)₂tren]的镜面对称性破缺: 螯环的特殊手性构象[J]. 物理化学学报, 2012, 28(02): 257-264.

LIU Cheng-Yong, YAN Jian-Xin, LIN Yi-Ji, LI Dan, FANG Xue-Ming, ZHANG Hui. Mirror Symmetry Breaking of cis-[Ni(NCS)₂tren]: Special Chiral Conformations of Chelate Rings[J]. Acta Phys. -Chim. Sin., 2012, 28(02): 257-264.

参考文献

(1) Santiago, A.; Pere, A.; David, A. Chem. Soc. Rev. 2005, 34 (4), 313.
(2) Brock, C. P.; Dunitz, J. D. Chem. Mater. 1994, 6 (8), 1187.
(3) Nagasato, S., Katsuki, I.; Motoda, Y.; Sunatsuki, Y.; Matsumoto, N.; Kojima, M. Inorg. Chem. 2001, 40 (11), 2534.
(4) Ikuko, K.; Naohide, M.; Masaaki, K. Inorg. Chem. 2000, 39 (15), 3350.
(5) Katsuki, I.; Motoda, Y.; Sunatsuki, Y.; Matsumoto, N.; Nakashima, T.; Kojima, M. J. Am. Chem. Soc. 2002, 124 (4), 629.
(6) Saha, M. K.; Fronczek, F. R.; Rees, L. H.; Bernal, I. Inorg. Chem . Commun. 2003, 6 (8), 983.
(7) Rao, A. S.; Pal, A.; Ghosh, R.; Das, S. K. Inorg. Chem. 2009, 48 (5), 1802.
(8) Purcell, K. F.; Kotz, J. C. Inorganic Chemistry;W. B. Saunders Company: Philadelphia, 1977; pp 642-644.
(9) Mason S. F. Molecular Optical Activity and the Chiral Discriminations; Cambridge University Press: Cambridge, 1982; Chapter 7.
(10) Zhang, H. Coordination Chemistry —Principles and Applications. Chemical Industry Press: Beijing, 2009. [章慧. 配位化学—原理与应用. 北京: 化学工业出版社, 2009.]
(11) Jin, D. M.; ZhuW. X. Study Methods of Coordination Chemistry. Science Press: Beijing, 1996; Chapter 7. [金斗满, 朱文祥. 配位化学研究方法. 北京: 科学出版社, 1996: 第七章.]
(12) Bosnich, B.; Harrowfield, J. M. J. Am. Chem. Soc. 1972, 94 (10), 3425.
(13) Aoki, T.; Matsumoto, K.; Ooi, S.; Kuroya, H. Bull. Chem. Soc. Jpn. 1973, 46, 159.

(14) Bernal, I. Inorg. Chim. Acta 1985, 96 (1), 99.
(15) Bernal, I.; Cetrullo, J. Inorg. Chim. Acta 1988, 150 (1), 75.
(16) Bernal, I.; Cetrullo, J. Inorg. Chem. 1993, 32 (19), 4098.
(17) Bernal, I.; Cetrullo, J. J. Coord. Chem. 1993, 28 (1), 89.
(18) Bernal, I.; Cetrullo, J.; Myrczek, J. J. Coord. Chem. 1993, 30 (1), 29.
(19) Bernal, I.; Myrczek, J.; Cai, J. Polyhedron 1993, 12 (10), 1149.
(20) Nakagawa, H.; Ohba, S.; Asakura, K.; Miura, T.; Tanaka, A.; Osanai, S. Acta Cryst. 1997, 53 (2), 216.
(21) Gerard, K. J.; Morgan, J.; Steel, P. J.; House, D. A. Inorg. Chim. Acta 1997, 260 (1), 27.
(22) Bernal, I.; Somoza, F.; Chen, Y. C.; Massoud, S. S. J. Coord. Chem. 1997, 41 (3), 233.
(23) Bose, D.; Rahaman, S. H.; Ghosh, R.; Mostafa, G.; Ribas, J.; Hung, C. H.; Ghosh, B. K. Polyhedron 2006, 25 (3), 645.
(24) Nie, F. M.; Dong, Z. Y. J. Chem. Crystallogr. 2011, 41 (1), 1.
(25) Wang, Y.;Wang, Y. K.;Wang, J. M.; Liu, Y.; Yang, Y. T. J. Am. Chem. Soc. 2009, 131 (25), 8839.
(26) Richardson, F. S. Chem. Rev. 1979, 79 (1), 17.
(27) Okawa, H. Coord. Chem. Rev. 1988, 92, 1.

(28) Ziegler, M.; von Zelewsky, A. Coord. Chem. Rev. 1998, 177 (1), 257.
(29) Davis, A. V.; Fiedler, D.; Ziegler, M.; Terpin, A.; Raymond, K. N. J. Am. Chem. Soc. 2007, 129 (49), 15354.
(30) Dwyer, F. P.; Garvan, F. L.; Shulman, A. J. Am. Chem. Soc. 1959, 81 (2), 290.
(31) McCaffery, A. J.; Mason S. F.; Norman, B. J. Chem. Commun. 1965, No. 1, 49.
(32) Bosnich, B.; Sullivan, E. A. Inorg. Chem. 1975, 14 (11), 2768.
(33) Zhou, N.;Wan, S. G.; Zhao, J.; Lin, Y. J.; Xuan,W. M.; Fang, X. M.; Zhang, H. Science in China Series B : Chemistry 2009, 52 (11), 1851.
(34) Lin, Y. J.;Wan, S. G.; Zou, F.;Wang, Y. K.; Zhang, H. New J. Chem. doi: 10.1039/C1NJ20430K.
(35) Richard, M. H.; Rob, S. Inorg. Chem. 2009, 48 (21), 10476.
(36) Ding, L.; Lin, L. R.; Liu, C. Y.; Li, H. K.; Qin, A. J.; Liu, Y.; Song, L.; Zhang, H.; Tang, B. Z.; Zhao, Y. F. New J. Chem. 2011, 35 (9), 1781.
(37) Pescitelli, G.; Kurtán, T.; Florke, U.; Kröhn, K.; Krohn, K. Chirality 2009, 21 (1E), E181.
(38) Kuroda, R.; Honma, T. Chirality 2000, 12 (6), 269.
(39) Spitz, C.; Dähne, S. J. Phys. Chem. B 2000, 104 (36), 8664.
(40) Castiglioni, E.; Biscarini, P.; Abbate, S. Chirality 2009, 21 (1E), E28.
(41) Bilotti, I.; Biscarini, P.; Castiglioni, E.; Ferranti, F.; Kuroda, R. Chirality 2002, 14 (9), 750.
(42) Minguet, M.; Amabilino, D. B.;Wurst, K.; Veciana, J. J. Chem. Soc. Perkin Trans 2 2001, 5, 670.
(43) Zhang, H.; Chen, Y. C.;Wang, F.; Qiu, X. M.; Li, L.; Chen, J. G. Acta Phys. -Chim. Sin. 2006, 22 (6), 666. [章慧, 陈渊川, 王芳, 邱晓明, 李丽, 陈坚固. 物理化学学报, 2006, 22 (6), 666.]
(44) Sheldrick, G. M. SHELXS97 and SHELXL97; University of Göttingen: Germany, 1997.
(45) Farrugia, L. J. J . Appl . Cryst. 1999, 32, 837.

(46) Farrugia, L. J. J . Appl . Cryst. 1997, 30, 657.
(47) Wang, F.; Zhang, H.; Li, L.; Hao, H. Q.;Wang, X. Y.; Chen, J. G. Tetrahedron: Asymmetry 2006, 17 (14), 2059.
(48) Lever, A. B. P. Inorganic Electronic Spectroscopy, 2nd ed.; Elsevier Science: New York, 1984; 507-520.
(49) Lennartson, A.; Vestergren, M.; Hakansson, M. Chem. Eur. J. 2005, 11 (6), 1757.

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cis-[Ni(NCS)₂tren]的镜面对称性破缺: 螯环的特殊手性构象

Mirror Symmetry Breaking of cis-[Ni(NCS)₂tren]: Special Chiral Conformations of Chelate Rings

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