中文摘要
本项目开展了吡唑烷的功能化及相关反应研究。重点研究了有机锡功能化的双吡唑甲烷，桥头碳上杂原子功能化的双吡唑烷以及混合吡唑烷的修饰及反应。通过有机锡功能化的双吡唑甲烷与羰基钼（钨）的反应，制得了结构新颖的四元金属杂环化合物，并考查了它们与各种亲电和亲核试剂的反应活性。桥头碳上杂原子功能化的双吡唑烷也表现出了新颖的反应活性，依赖于不同的金属，这些配体可以单齿，双齿以及三齿的方式与金属作用。用其它的含氮杂环如咪唑，三唑、吡啶等取代一个吡唑所形成的混合吡唑烷类配体的修饰结果表明，这些混合吡唑烷类配体的反应性显著的不同于双吡唑甲烷。如双(1-甲基咪唑-2-基)甲基负离子并不与三烷基氯化锡反应，形成有机锡功能化的衍生物。而有机锡功能化的1-(2-吡啶基)硫代甲基-(3,5-二甲基)吡唑与羰基钼反应所得到的四元金属杂环化合物的反应活性显著的不同于类似的双吡唑甲烷衍生物。当用亲核试剂如亚磷酸酯处理这些四元金属杂环时，前者发生分子内的重排，异构化为吡啶基硫酮的形式与金属作用，而后者发生P-O/C键交换反应, 导致还原消除, 得到中性的三齿配位化合物。我们也对以上一些新颖反应的机理进行了初步的探讨。
英文摘要
In this project, functionalized bis(pyrazol-1-yl)methane especially by the organotin groups and heteroatoms on the bridging carbon atom, as well as the modification of mixed pyridyl or imidazolylpyrazolylmethanes, and their related reactions have been investigated. Some four-membered heterometallacycles with M-Sn (M = Mo or W) bonds have been obtained by the reaction of bis(pyrazol-1-yl)methanes or mixed pyridyl pyrazolylmethanes functionalized by organotin groups with carbonyl molybdenum (tungsten). We deeply study the reactivity of these novel heteronuclear complexes, and find that they provide unusual reactivity upon treatment with electrophilic (such as SnCl4) or nucleophilic (such as PR3) reagents. In addition, we also investigate the interaction between bis(pyrazol-1-yl)methide anoin with various electrophiles to form NEN multidentate ligands, and study their reactions with main group and transition metals. We find that these founctionlized bis(pyrazol-1-yl)methanes by heteroatoms on the bridging carbon atom are able to act as a monodentate, bidentate and tridentate ligand, depending on different metal atoms. Prelimary investigations show the reactivity of mixed pyridyl or imidazolylpyrazolylmethanes is markedly different from that of the corresponding bis(pyrazol-1-yl)methanes. For example, the reaction of bis(1-methylimidazole-2-yl)methide with Ph3SnCl does not take place. While the reactivity of the four-membered heterometallacycle, formed by the reaction of 1-(2-pyridyl)thiomethyl-(3,5-dimethyl)pyrazole modified by triphenylstannyl with carbonyl molybdenum, is different from that of the analog of bis(pyrazol-1-yl)methanes. The former arranges to result in a C=S coordination mode upon treatment with PR3, while the latter leads to unexpected P-O/C exchange reactions with the cleavage of M-C bond to give the reductive elimination product. The related reaction mechanisms are also discussed.
结题摘要
本项目开展了吡唑烷的功能化及相关反应研究。重点研究了有机锡功能化的双吡唑甲烷，桥头碳上杂原子功能化的双吡唑烷以及混合吡唑烷的修饰及反应。通过有机锡功能化的双吡唑甲烷与羰基钼（钨）的反应，制得了结构新颖的四元金属杂环化合物，并考查了它们与各种亲电和亲核试剂的反应活性。桥头碳上杂原子功能化的双吡唑烷也表现出了新颖的反应活性，依赖于不同的金属，这些配体可以单齿，双齿以及三齿的方式与金属作用。用其它的含氮杂环如咪唑，三唑、吡啶等取代一个吡唑所形成的混合吡唑烷类配体的修饰结果表明，这些混合吡唑烷类配体的反应性显著的不同于双吡唑甲烷。如双(1-甲基咪唑-2-基)甲基负离子并不与三烷基氯化锡反应，形成有机锡功能化的衍生物。而有机锡功能化的1-(2-吡啶基)硫代甲基-(3,5-二甲基)吡唑与羰基钼反应所得到的四元金属杂环化合物的反应活性显著的不同于类似的双吡唑甲烷衍生物。当用亲核试剂如亚磷酸酯处理这些四元金属杂环时，前者发生分子内的重排，异构化为吡啶基硫酮的形式与金属作用，而后者发生P-O/C键交换反应, 导致还原消除, 得到中性的三齿配位化合物。我们也对以上一些新颖反应的机理进行了初步的探讨。