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化学学报
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化学学报 ›› 2013, Vol. 71 ›› Issue (10): 1373-1378.DOI: 10.6023/A13060683 上一篇    下一篇

研究论文

由钌杂s-顺丁二烯化合物合成钌杂多环配合物的研究

张春红, 张弘, 魏爱琳, 何旭敏, 夏海平   

  1. 厦门大学化学化工学院 厦门 361005
  • 投稿日期:2013-06-30 发布日期:2013-07-19
  • 通讯作者: 夏海平,E-mail:hpxia@xmu.edu.cn;何旭敏,E-mail:hejin@xmu.edu.cn;Tel.:0592-2186658 E-mail:hpxia@xmu.edu.cn;hejin@xmu.edu.cn
  • 基金资助:

    项目受国家重点基础研究发展计划(No. 2012CB821600)、国家自然科学基金(Nos. 20925208, 21174115, 21272193)及长江学者和创新团队发展计划资助.

Synthesis of Ruthena-polycyclic Complexes by Ruthenium-Vinylcarbene Complex

Zhang Chunhong, Zhang Hong, Wei Ailin, He Xumin, Xia Haiping   

  1. College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005
  • Received:2013-06-30 Published:2013-07-19
  • Supported by:

    Project supported by the National Basic Research Program of China (No. 2012CB821600), the National Natural Science Foundation of China (Nos. 20925208, 21174115, 21272193) and the Program for Changjiang Scholars and Innovative Research Team in University.

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研究了配位不饱和的钌杂s-顺丁二烯化合物[Ru(CHC(PPh3)CH(2-Py))Cl2PPh3]BF4 (1)与水、甲醇、苯胺和2-巯基吡啶等亲核试剂的[4+1]关环反应, 合成了一系列有趣的钌杂多环化合物[Ru(CHC(PPh3)CHR(2-Py))Cl(PPh3)2]BF4 [R=OH (2), OMe (3), 和NHPh (4)]与[Ru(CHC(PPh3)CH(S(2-Py))(2-Py))PPh3(S(2-Py)]BF4 (5). 此外, 将配位不饱和的钌配合物1与三苯基膦配体反应, 制备了类似于氮杂金属萘的配位饱和化合物[Ru(CHC(PPh3)CH(2-Py))Cl2(PPh3)2]BF4 (6). 6与HBF4反应可生成金属杂环结构类似的分子内含三氯桥的双钌核配合物[{Ru(CHC(PPh3)CH(2-Py))PPh3}2(μ-Cl)3](BF4)3 (7). 以上产物均通过核磁(NMR)与元素分析进行了表征, 并解析了部分产物的X射线单晶结构.

关键词: 钌卡宾, 烯基卡宾, 钌杂多环化合物, 亲核加成, [4+1]关环

Treatment of ruthenium-vinylcarbene complex[Ru(CHC(PPh3)CH(2-Py))Cl2PPh3]BF4 (1) and PPh3 with nucleophilic reagents H2O, CH3OH, NH2Ph, or 2-mercaptopyridine led to the ruthena-polycyclic complexes[Ru(CHC(PPh3)-CHR(2-Py))Cl(PPh3)2]BF4[R=OH (2), R=OCH3 (3), R=NHPh (4)] or[Ru(CHC(PPh3)CH(S(2-Py))(2-Py))PPh3-(S(2-Py)]BF4 (5). They are stable under air at solid state. CH3OH in the reaction is not only the reagent but also the solvent and the reaction must be heated at 60 ℃ for 6 h. All the other reactions were carried out at room temperature in CH2Cl2. The crystals of 4 and 5 were grown from CH2Cl2 and CHCl3 solutions layered with diethyl ether, respectively. The structures 4 and 5 were determined by X-ray crystallography. The crystal size of 4 is a=1.29145(3) nm, b=1.37687(5) nm, c=1.86914(4) nm, α=92.114(2)°, β=106.271(2)°, γ=96.333(3)° and the size of 5 is a=1.15333(18) nm, b=1.20072(19) nm, c=1.9081(3) nm, α=88.466(3)°, β=87.918(3)°, γ=79.521(3)°. In addition, refluxing 1 with PPh3 in CHCl3 for 6 h to produce red solid[Ru(CHC(PPh3)CH(2-Py))Cl2(PPh3)2]BF4 (6). The reaction of complex 6 with HBF4 at room temperature for 3 h afforded the (μ-Cl)3-bridged bisruthenium-vinylcarbene complex[{Ru(CHC(PPh3)CH(2-Py))PPh3}2(μ-Cl)3](BF4)3 (7) in 87% yield. The crystal of 6 was grown from CH3COCH3 solution layered with diethyl ether, and the crystal of 7 was grown from CHCl3 solution layered with diethyl ether. The structures of 6 and 7 were also determined by X-ray crystallography. The crystal size of 6 and 7 are a=1.13777(3) nm, b=1.56466(7) nm, c=1.79541(7) nm, α=75.822(3)°, β=79.502(2)°, γ=79.259(3)°, a=1.68830(3) nm, b=2.33421(4) nm, c=2.48603(4) nm, α=90°, β=96.5530(10)°, γ=90°, respectively. The CCDC number for 3, 5, 6, and 7 are 945539 (3), 945538 (5), 945541 (6), and 945542 (7). All these complexes were fully characterized by elemental analysis and NMR spectroscopy.

Key words: ruthenium carbene, vinylcarbene, ruthena-polycyclic complex, nucleophilic addition, [4+1] cycloaddition