含二硒磷酸配位基之鉬錯合物的化學

The chemistry of molybdnum complexes containing Diselenophosphate ligands

莊欽委(Chin-Wei Chuang)

指導教授 ： 劉鎮維

中原大學/理學院/化學研究所/碩士(2003年)

https://doi.org/10.6840/cycu200300529

摘要

中文摘要

化合物1和化合物2可以從雙二硒磷酸配位基[-(Se)SeP(OC3H7)2]2和Mo(CO)6以甲苯為溶劑在110℃時反應得到，化合物1是以1：3的比例反應得到。化合物1是一個三核鉬的金屬簇[Mo3(μ3-Se)(μ2-Se2)3{Se2P(OC3H7)2}3][Cl]。使用2：3的比例反應，我們可以得到一個四核鉬的金屬簇， Mo4(μ3-Se)4[Se2P(OC3H7)2]6。化合物2的結構為一個有輕微扭曲的Mo4-Se4立方體，且在立方體中的每兩個金屬上有一個二硒磷酸配位基以架橋的形式作為連接。此外，使用17個電子的自由基CpMo(CO)3‧與雙二硒磷酸配位基[-(Se)SeP(OC3H7)2]2在室溫下反應，可以得到三個化合物：3, CpMo(CO)2[Se2P(OC3H7)2]、4, (CpMo)2{μ-Se3P(Se)(OC3H7)2}2 和5, (CpMo)2{μ-Se3P(O)(OC3H7)2}2。我們還發現了一個有趣的現象， 化合物3會反應轉變為化合物5，且化合物4為這個反應的中間產物。這些化合物的特性由元素分析儀、FAB質量分析儀、NMR光譜儀{1H, 31P, 77Se}與X-ray單晶繞射儀所鑑定完成。

關鍵字

二硒磷酸配位基之鉬錯合物

並列摘要

Abstract

Two types of products (1 and 2) were isolated from the reaction of bis(selenophpsphoryl) diselenides [-(Se)SeP(OC3H7)2]2 and Mo(CO)6 in toluene at 110℃. The compound 1 was formed using molar ratio of 3:1. The formulation of 1, is trinuclear-molybdenum cluster, [Mo3(μ3-Se)(μ2-Se2)3{Se2P(OC3H7)2}3][Cl]. Using the molar ratio of 3:2, tetranuclear-molybdenum Cluster, Mo4(μ3-Se)4[Se2P(OC3H7)2]6 was obtained. The geometry in 2 can be described as a slightly distorted Mo4-Se4 cube with each two metals of the cube being bridged by a selenium atom of the diselenophosphate ligand. In addition, we have a reaction of cyclopentadienyl molybdenum tricarbonyl 17-electron radical species,CpMo(CO)3．with bis(selenophpsphoryl) diselenides, [-(Se)SeP(OC3H7)2]2. In this reaction at ambient temperature, we obtained three compounds：3, CpMo(CO)2[Se2P(OC3H7)2]、4, (CpMo)2{μ-Se3P(Se)(OC3H7)2}2 and 5, (CpMo)2{μ-Se3P(O)(OC3H7)2}2. We can see a reaction where complex 3 changes to complex 5 and complex 4 is a intermediate product in this reaction. These complexes were characterized by element analyses, positive FAB mass spectrometry, multinuclear NMR (1H, 31P and 77Se), and X-ray diffraction.

並列關鍵字

Diselenophosphate ligands

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