第Ⅷ族钳形金属催化剂的研究进展

Development of Pincer Catalysts with Selected Group 8～10 Metals

钳形金属化合物在有机合成、有机金属催化以及材料科学等领域都有着重要的应用.主要总结了本课题组近几年来在第Ⅷ族钳形金属化合物的合成与催化应用方面取得的一些进展,包括利用廉价易得的原料、通过芳环的C—H键活化方法,合成得到多种非手性和手性的PCP钳形钯(Ⅱ)化合物、PCN钳形钯(Ⅱ)和镍(Ⅱ)化合物、双(咪唑啉)苯NCN钳形钯(Ⅱ)、铂(Ⅱ)、镍(Ⅱ)、铑(Ⅲ)和铱(Ⅲ)化合物、NCN'钳形钯(Ⅱ)化合物、CNN'钳形钯(Ⅱ)和钌(Ⅱ)化合物等,尤其是探索出的"一锅煮"的膦化/金属化反应,为多种类型PCP和PCN钳形金属化合物的合成提供了新的途径,该方法毋须分离不稳定的含膦配体,并成功地实现了相关配体中心芳环2位的C—H键活化,从而简化了合成步骤,使得操作简便易行、产物收率高.所得到的钳形金属化合物被用于催化多种碳-碳键生成反应(包括不对称的催化反应)、酮的氢转移反应、不对称膦氢化反应等.相关的文献报道也将做适当讨论.

Pincer metal complexes have been widely applied in organic synthesis, organometallic catalysis and materials sci- ence, In this account, we trace our studies on the synthesis of pincer complexes of selected group 8-10 metals and their ap- plications in catalytic reactions. Successful examples include achiral and chiral PCP pincer Pd（Ⅱ） complexes, PCN pincer complexes of Pd（Ⅱ） and Ni（Ⅱ）, bis（imidazolinyl）phenyl NCN pincer complexes of Pd（Ⅱ）, Pt（Ⅱ）, Ni（Ⅱ）, Rh（Ⅲ） and Ir（Ⅲ）, NCN＇ pincer Pd（Ⅱ） complexes and CNN＇ pincer complexes of Pd（II） and Ru（Ⅱ）, which are conveniently prepared from easily available starting materials via direct Caryl-H bond activation. Particularly, a one-pot phosphorylatiou/metalation strategy was developed, providing a new and facile approach for the preparation of PCP and PCN pincer metal complexes. The method avoids the troublesome isolation of the unstable ligands and meanwhile a^omplishes the metalation of the re- lated ligands central C--H bond in good yields, and the synthetic procedures are thus simplified. The obtained pincer metal complexes have been used as catalysts in various C-C bond-forming reasons including the asymmetric ones, transfer hy- drogenation of ketones and asyrmnetric hydrophosphination. The related literature results are also prestented.