磺酸酯功能化双吡唑烷的合成及其相关反应研究-有机化学专业论文.docxVIP

摘要摘要 摘要 摘要 由于其广泛的配位能力以及易于修饰，双吡唑甲烷受到了人们广泛的关 注。本论文开展了桥头碳上磺酸酯功能化双吡唑甲烷的合成及其相关反应研 究，并取得了如下的研究成果。 合成了对甲苯磺酸2,2．双(3，5．二甲基吡唑．1．基)乙酯，该化合物的反应活 性明显的依赖于外加试剂的亲核性与碱性。当试剂的碱性较强时易发生消除反 应得到1，1．双(3，5．二甲基吡唑．1．基)7--,烯，而当试剂(如苯硫酚负离子或有机胺) 的亲核性较强时，则易制得多功能化的双吡唑甲烷配体。 通过1，1．双(3，5．二甲基吡唑一1．基)乙烯的锡氢化反应，制得了一类有机锡 功能化的双吡唑甲烷配体，并研究了其与w(co)6的反应。实验结果表明，无 论锡原子上的取代基为芳基或烷基，都能实现Sn．C(sp3)键对钨中心的氧化加 成作用，这与以前的研究发现显著的不同，以前的研究表明仅有芳基锡修饰的 双吡唑甲烷才能发生类似的反应。 为了考查其他结构类似的配体如双咪唑甲烷以及双吡啶甲烷衍生物是否 也能发生相关的反应，我们合成了结构类似的有机锡修饰的双咪唑甲烷及双吡 啶甲烷，并研究了它们与w(co)6的反应。结果表明，没有发生Sn．C(sp3)键对 钨中心的氧化加成作用，只发生了脱羰基反应。 考查了硫、氮等功能化的双吡唑甲烷配体的配位能力。通过与M(CO)6(M =W或Mo)反应分别制得了结构新颖的K3．IN，N，N]和K3．[N，S，N】型配合物。 关键词：双吡唑甲烷；氧化加成；锡氢化反应；羰基钨 AbstractAbstract Abstract Abstract Bis(1：Iyrazol-l—y1)methane have been of considerable interest owing to its wide range of coordination capabilities and ease to be modificated，The synthesis and reactivities of bis(pyrazol-1-y1)alkanes modificated by sulfonate groups on the bridging carbon atom Was carry out in this thesis．The following research results have been obtained． A series of bis(pyrazol—·1··y1)alkane ligands modificated by organotin WaS synthesized by the hydrostannylation of 2，2-bis(3，5-dimethyl—pyrazole-1-y1)ethylene． The reactions of these ligands with w(co)6 has been investigated in detail． Experimental results show that oxidative addition of the Sn-C(sp3)bond to the tungsten(O)center happens no matter the tin atom has electron withdrawing phenyl or electron donating benzyl and butyl groups on．Further studies were carried out using moieties such as imidazole and pyridine instead of pyrazole ring to understand the influence of inductive effect．The reaction of these ligands、航m w(co)6 only gave the decarbonylation complex，while no oxidative addition product of me sn—c(s，) bond to the tungsten(O)center Was observed． Coordination capabilities of sulfur and nitrogen functioned Bis(pyrazol一1-y1)methane ligand have been investigated，the reaction of these ligands with M(CO)6(M=W／Mo)resulted in corresponding Kj-[N，N，N]and Kj