苯環金屬烯的反應性探討

Abstract

碳烯的重類似物近年來受到越來越多的關注，取代碳異環碳烯(N-heterocyclic carbene)中的碳原子成重十四族的元素也發現了許多出乎預期的反應。在本篇論文中合成了單牙及三牙的金屬烯配位基，在單牙的鍺烯與錫烯與零價鈀金屬的反應中成功的分離出雙鍺烯、錫烯鈀金屬錯化合物，然而在與鉛烯的反應中，則觀察到了氧化反應的發生而不是與金屬形成錯化合物。此外，我們也利用三牙的鍺烯配位基合成了具有未鍵結磷配位基的釕金屬錯化合物，此錯化合物也可以當作一個特別的骨架去合成同核及異核雙金屬錯化合物。且單核及雙核的釕金屬錯化合物在吡啶的硼氫化反應中也表現出不同反應的活性與選擇性。

Being the heavier analogue of N-heterocyclic carbene, NHE (E = Si, Ge, Sn, Pb) metallylenes have received more and more attention recently. Substituting the central divalent carbon of N-heterocyclic carbene with heavier group 14 elements has led to the discovery of several unexpected reactions in the past few years. In this study, pincer type PEP and monodentate metallylene were synthesized and isolated. The coordination chemistry of N,N-dimesityl-substituted benzannulated germylene and stannylene towards Pd0 complex are investigated. However, exploring reactivity of plumbylene ,We observed NMR-active and paramagnetic products in the oxidation reaction. Additionally, The coordination of a P-Ge-P tridendent pincer ligand bearing a germylene coordination site toward ruthenium complex was investigated. The resulting unsymmetrical phosphine-germyl complex of Ru featuring a uncoordinated phosphine side-arm turns out to be an intriguing platform for constructing bimetallic system including Ru-Ru and Ru-Au systems. Catalytic performance of the mono- and bi-metallic Ru(arene)PGeP based complexes in hydroboration of pyridine was also examined.