一氧化碳的錳金屬化合物與氮的碳烯雜環(NHCs)及磷配位基(PR3)的合成與鑑定

Synthesis and Charactrization of Manganese(I) Carbonyl N-Heterocyclic Carbenes(NHCs) / Phosphine(PR3) Complexes.

黃柏瑋(Po-Wei Huang)

指導教授 ： 謝忠宏

淡江大學/理學院/化學學系碩士班/碩士(2016年)

https://doi.org/10.6846/TKU.2016.00857

摘要

本論文主要在探討一氧化碳的錳金屬化合物，分別與氮的碳烯雜環(NHCs) 及磷配位基(PR3)的合成與鑑定，我們藉由合成不同配位基的一氧化碳錳金屬化合物MnBr(CO)4NHC (4) 與MnBr(CO)4PPh3 (5)，或者不同配位基數目的錳金屬化合物MnBr(CO)4PPh3 (5) 與MnBr(CO)4(PPh3)2 (6)，來瞭解這些化合物鍵長、鍵角的差異與特性，利用紅外線光譜儀以及X光單晶繞射儀來確認反應是否完全和解析結構。而我們也合成了其他錳金屬化合物MnBr2(PPh3)2 (8)，來與小分子氣體(例如：氧氣、一氧化氮)來形成化合物MnBr2(OPPh3)2 (9)、MnBr2(PPh3)2NO (10)，我們未來的目標希望在催化反應上使用含氮異環碳烯的錯化合物來取代磷配位基錯化合物，並且嘗試小分子的活化反應。

關鍵字

錳金屬化合物 ； 氮的碳稀雜環 ； 磷配位基

並列摘要

N-Heterocyclic carbenes(NHCs) is an important ligands in organometallic chemistry. The NHCs are electron-rich; good σ-donor ligands, and the donating ability of NHCs can be altered by modified the azole ring. The NHCs can effective bind to matal to give a stabe structure. As well as NHCs , Phosphine (PR3) ligands is a σ-donor , the donating ability can be tuned by the cone angles. Therefore, we can modify the steric and electron effect of N-Heterocyclic carbenes and Phosphine ligands. When it coordinated to metal center. In this study, The Bis(pentacarbonylmanganese)(Mn2(CO)10) with Br2 were treated with dichloromethane to afford the precursors Mn(CO)5Br. The precursor reacted with N-Heterocyclic carbenes (NHCs) / Phosphine(PR3) ligands in tetrahydrofuran to form the mononuclear complexes MnBr(CO)4L(L = NHCs (4) , PR3 (5)). Complex 5 reacted with 1 equiv of Phosphine ligands in tetrahydrofuran to form the complex MnBr(CO)4(PPh3)2 (6). Nitric oxide was introduced to the THF solution of complex 6, Complex Mn(NO)2Br(PPh3)2 (7) was formed. Complexes 4, 5, 6 and 7 were purfied with column chromatography and characterized by X-ray diffractometer and IR analyses.
In addition, the Manganese(II) bromide were treated with Phosphine ligands to afford the complex MnBr2(PPh3)2 (8). Complex 8 reacted with small molecular gases (eg： oxygen、nitric oxide) to form the complexes MnBr2(OPPh3)2 (9) and complex MnBr2(PPh3)2NO (10) respectively. Our future goal is to use NHCs instead of Phosphine ligands for catalytic reaction and to exam the activation reaction of small moleculars.

並列關鍵字

Manganese ； N-Heterocyclic Carbenes(NHCs) ； Phosphine(PR3) ； small molecular

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