Synthesis of Ruthena-polycyclic Complexes by Ruthenium-Vinylcarbene Complex

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.Treatment of ruthenium-vinylcarbene complex [Ru(CHC(PPh3)CH(2-Py))Cl2 PPh3 ]BF4(1) and PPh3 with nucleophilic reagents H2 O,CH3 OH,NH2 Ph,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.CH3 OH 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 CH2 Cl2 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 CH3 COCH3 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.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); 长江学者和创新团队发展计划资助~

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