[RuCl2＝CH(o-C6H4X)(PCy3)2](X=F, Cl, Br)的合成和催化性能研究

摘要合成了一类苄亚基钌邻位含卤素的钌卡宾烯烃复分解催化剂[RuCl₂＝CH(o-C₆H₄X)(PCy₃)₂][X=F (10),Cl (11),Br (12)],并采用核磁共振波谱确定了结构。在25 ℃下,催化剂表现出良好的稳定性。30 ℃下,以二烯丙基丙二酸二乙酯为关环复分解反应(RCM)模型进行了动力学研究,结果表明催化剂10具有较快的引发速率,在40 min后底物转化率可达到70%。测试了其对不同底物的催化效果,发现3种催化剂皆具有较强的官能团适用性,可以催化关环复分解和交叉复分解反应(CM)。

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	吴夏芊
	杨鲜锋
	毕淑梦
	马朋
	王建辉

关键词：钌卡宾配合物烯烃复分解关环复分解交叉复分解

Abstract： A series of ruthenium carbene olefin metathesis catalysts [RuCl₂＝CH(o-C₆H₄X)(PCy₃)₂] (X=F (10), Cl (11), Br (12)) were synthesized and characterized by means of nuclear magnetic resonance spectrometry. The catalysts showed relatively high stability. Kinetic studies on the ring-closing metathesis (RCM) of diethyl diallylmalonate showed that high initiation rate and high final conversion were obtained by using catalyst 10. These catalysts were found to be effective in ring-closing metathesis and cross metathesis and exhibited remarkable functional group tolerance.

Keywords： Ru carbene complexes olefin metathesis ring closing metathesis cross metathesis

Received 2022-02-16;

Fund:国家自然科学基金项目(22071177)。

Corresponding Authors: 王建辉,教授,E-mail:wjh@tju.edu.cn。 Email: wjh@tju.edu.cn

About author: 吴夏芊(1998-),女,硕士研究生,现从事有机催化方面的研究。

引用本文:

吴夏芊, 杨鲜锋, 毕淑梦, 马朋, 王建辉.[RuCl₂＝CH(o-C₆H₄X)(PCy₃)₂](X=F, Cl, Br)的合成和催化性能研究[J]. 化学工业与工程, 2024,41(4): 38-44

WU Xiaqian, YANG Xianfeng, BI Shumeng, MA Peng, WANG Jianhui.Synthesis of [RuCl₂＝CH(o-C₆H₄X)(PCy₃)₂](X=F, Cl, Br) andits applications in olefin metathesis reactions[J]. Chemcial Industry and Engineering, 2024,41(4): 38-44

[1] 杜创, 王春雨, 张国, 等. 降冰片烯开环易位聚合反应的分子量及分子量分布控制[J]. 高等学校化学学报, 2007, 28(10): 2018-2020 DU Chuang, WANG Chunyu, ZHANG Guo, et al. Molecular weight and molecular weight distribution control of ring-opening metathesis polymerization of norbornene[J]. Chemical Journal of Chinese Universities, 2007, 28(10): 2018-2020(in Chinese)
[2] VOUGIOUKALAKIS G C, GRUBBS R H. Ruthenium-based heterocyclic carbene-coordinated olefin metathesis catalysts[J]. Chemical Reviews, 2010, 110(3): 1746-1787
[3] HOVEYDA A H, ZHUGRALIN A R. The remarkable metal-catalysed olefin metathesis reaction[J]. Nature, 2007, 450: 243-251
[4] MORZYCKI J W. Application of olefin metathesis in the synthesis of steroids[J]. Steroids, 2011, 76(10/11): 949-966
[5] MOL J C. Application of olefin metathesis in oleochemistry: An example of green chemistry[J]. Green Chemistry, 2002, 4(1): 5-13
[6] HERBERT M B, MARX V M, PEDERSON R L, et al. Concise syntheses of insect pheromones using Z-selective cross metathesis[J]. Angewandte Chemie (International Ed in English), 2013, 52(1): 310-314
[7] TRNKA T M, GRUBBS R H. The development of L₂X₂RuCHR olefin metathesis catalysts: an organometallic success story[J]. Accounts of Chemical Research, 2001, 34(1): 18-29
[8] SCHROCK R R, DEPUE R T, FELDMAN J, et al. Preparation and reactivity of several alkylidene complexes of the type W(CHR’)(N-2,6-C₆H₃-iso-Pr₂)(OR)₂ and related tungstacyclobutane complexes. Controlling metathesis activity through the choice of alkoxide ligand[J]. Journal of the American Chemical Society, 1988, 110(5): 1423-1435
[9] SCHOETTEL G, KRESS J, OSBORN J A. A simple route to molybdenum-carbene catalysts for alkene metathesis[J]. J Chem Soc, Chem Commun, 1989(15): 1062-1063
[10] NGUYEN S T, JOHNSON L K, GRUBBS R H, et al. Ring-opening metathesis polymerization (ROMP) of norbornene by a Group VIII carbene complex in protic media[J]. Journal of the American Chemical Society, 1992, 114(10): 3974-3975
[11] SCHWAB P, GRUBBS R H, ZILLER J W. Synthesis and applications of RuCl₂(CHR’)(PR₃)₂: The influence of the alkylidene moiety on metathesis activity[J]. Journal of the American Chemical Society, 1996, 118(1): 100-110
[12] RUFINO-FELIPE E, VALDÉS H, GERMÁN-ACACIO J M, et al. Fluorinated N-heterocyclic carbene complexes. applications in catalysis[J]. Journal of Organometallic Chemistry, 2020, 921: 121364
[13] SCHOLL M, DING S, LEE C W, et al. Synthesis and activity of a new generation of ruthenium-based olefin metathesis catalysts coordinated with 1, 3-dimesityl-4, 5-dihydroimidazol-2-ylidene ligands[J]. Organic Letters, 1999, 1(6): 953-956
[14] LOVE J A, MORGAN J P, TRNKA T M, et al. A practical and highly active ruthenium-based catalyst that effects the cross metathesis of acrylonitrile[J]. Angewandte Chemie (International Ed in English), 2002, 41(21): 4035-4037
[15] CHOI T L, GRUBBS R H. Controlled living ring-opening-metathesis polymerization by a fast-initiating ruthenium catalyst[J]. Angewandte Chemie (International Ed in English), 2003, 42(15): 1743-1746
[16] LEITGEB A, WAPPEL J, SLUGOVC C. The ROMP toolbox upgraded[J]. Polymer, 2010, 51(14): 2927-2946
[17] SCHROCK R R. Synthesis of stereoregular polymers through ring-opening metathesis polymerization[J]. Accounts of Chemical Research, 2014, 47(8): 2457-2466
[18] 王晋宇, 柳春丽, 陈延辉. 胺基膦钌卡宾化合物的合成及催化烯烃复分解反应[J]. 高等学校化学学报, 2020, 41(12): 2766-2773 WANG Jinyu, LIU Chunli, CHEN Yanhui. Synthesis of aminophosphine ruthenium carbene complex and its application in olefins metathesis reaction[J]. Chemical Journal of Chinese Universities, 2020, 41(12): 2766-2773(in Chinese)
[19] LYNN D M, GRUBBS R H. Novel reactivity of ruthenium alkylidenes in protic solvents: Degenerate alkylidene proton exchange[J]. Journal of the American Chemical Society, 2001, 123(14): 3187-3193
[20] STEWART I C, BENITEZ D, O’LEARY D J, et al. Conformations of N-heterocyclic carbene ligands in ruthenium complexes relevant to olefin metathesis[J]. Journal of the American Chemical Society, 2009, 131(5): 1931-1938
[21] CHU C, LIN T, SHAO H, et al. Disentangling ligand effects on metathesis catalyst activity: Experimental and computational studies of ruthenium-aminophosphine complexes[J]. Journal of the American Chemical Society, 2018, 140(16): 5634-5643
[22] DUAN Y, WANG T, XIE Q, et al. Highly efficient nitrogen chelated ruthenium carbene metathesis catalysts[J]. Dalton Transactions, 2016, 45(48): 19441-19448
[23] HONG S, WENZEL A G, SALGUERO T T, et al. Decomposition of ruthenium olefin metathesis catalysts[J]. Journal of the American Chemical Society, 2007, 129(25): 7961-7968
[24] RITTER T, HEJL A, WENZEL A G, et al. A standard system of characterization for olefin metathesis catalysts[J]. Organometallics, 2006, 25(24): 5740-5745