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))C12PPh3]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-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))C12(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(co,1fBF4),(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))C12PPh3JBF4 (1) and PPh3 with nu cleophilic reagents H20, CH3OH, NHEPh, or 2-mercaptopyridine led to the ruthena-polycyclic complexes [Ru(CHC(PPh3)- CHR(2-Py))CI(PPh3)z]BF4 [R----OH (2), R= OCH3 (3), R=NHPh (4)] or [Ru(CHC(PPha)CH(S(2-Py))(2-Py))PPha- (S(2-Py)]BF4 (5). They are stable under air at solid state. CHaO°H in the reaction is not only the reagent but also the solvent and the reaction must be heated at 60 °C for 6 h. All the other reactions were carried out at room temperature in CH2C12. The crystals of 4 and 5 were grown from CH2C12 and CHCI3 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, a=92.114(2)°, y=106.271(2)°, y=96.333(3)° and the size of 5 is a= 1.15333(18) nm, b= 1.20072(19) nm, y=-1.9081(3) nm, a=88.466(3)°, β=87.918(3)°, 7=79.521(3)°. In addition, refluxing 1 with PPh3 in CHC13 for 6 h to pro- duce red solid [Ru(CHC(PPh3)CH(2-Py))C1E(PPh3)2]BF4 (6). The reaction of complex 6 with HBF4 at room temperature for 3 h afforded the (a-C1)a-bridged bisruthenium-vinylcarbene complex [{Ru(CHC(PPha)CH(2-Py))PPh3}E(fl-C1)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 CHC13 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, a=75.822(3)°, β=79.502(2)°, y=79.259(3)°, y=1.68830(3) nm, b=2.33421(4) nm, c=2.48603(4) nm, a=90°, β=96.5530(10)°, 7=90°, respectively. The CCDC number for 3, 5, 6, and 7 are 945539 (3), 945538 (5), 945541 (6?