含二硒磷酸配位基之汞、錫金屬錯合物的合成及鐵金屬錯合物的甲基化反應

Synthesis of Mercury and Tin complexes containing Dialkyl Diselenophosphate Ligands ＆ Methylation of Iron complex

劉紘源(Hung-Yuan Liu)

指導教授 ： 劉鎮維

中原大學/理學院/化學研究所/碩士(2004年)

https://doi.org/10.6840/cycu200400566

摘要

本次實驗利用二硒磷酸配位基NH4Se2P(OR)2（dialkyl diselenophosphate ligand）（R＝iPr, Et, nPr）與不同的金屬起始物進行反應，採用的金屬起始物為Hg(ClO4)2以及(C6H5)3SnCl。而之前本實驗室合成之鐵金屬錯合物Cp(CO)2FeP(Se)(OR)2（Cp＝η5-C5H5）（R＝iPr, Et, nPr），則嘗試甲基化之反應，試圖於硒原子上連接一個甲基。
NH4Se2P(OR)2與Hg(ClO4)2於室溫下以CH3OH為溶劑反應，可以獲得[Hg{Se2P(OR)2}2]n（R＝iPr, Et, nPr），為聚合物型態。
NH4Se2P(OR)2與(C6H5)3SnCl於低溫下以diethyl ether為溶劑反應，可以獲得(C6H5)3SnSe2P(OR)2（R＝iPr, Et, nPr）。
鐵金屬起始物Cp(CO)2FeP(Se)(OR)2的甲基化反應則是與(CH3)3OBF4於室溫下以CH2Cl2為溶劑反應，可以成功接上一個甲基，即獲得[Cp(CO)2FeP(SeCH3)(OR)2]BF4（R＝iPr, Et, nPr）。

關鍵字

二硒磷酸配位基 ； 甲基化反應 ； 汞金屬錯合物 ； 錫金屬錯合物 ； 鐵金屬錯合物

並列摘要

Compounds [Hg{Se2P(OR)2}2]n (R＝iPr, Et, nPr,) were synthesized from the reaction of Hg(ClO4)2•xH2O and NH4Se2P(OR)2 in a molar ratio of 1:2 in methanol at ambient temperature. The complexes were characterized by 1H, 31P NMR and by elemental analysis. For iso-propyl derivative the structure was determined by single crystal X-ray crystallography. X-ray analysis reveals that the structure is polymeric via bridging ligands and each Hg atom is coordinated by an addational chelating ligand. The Hg atom is connected by four selenium atoms in a distorted tetrahedral geometry.
Complexes (C6H5)3SnSe2P(OR)2 (R＝iPr, Et, nPr) were prepared from reaction of (C6H5)3SnCl and NH4Se2P(OR)2 in a molar ratio of 1:1 in diethyl ether at 0 °C. The complexes were characterized by 1H, 31P NMR and by elemental analysis. The ethyl and propyl derivatives were structurally characterized. The X-ray structure consists of three phenyl rings connected to Sn atom and a selenium atom from diselenophosphate ligand is also coordinated to Sn atom. The other selenium atom of diselenophosphate ligand is dangling. The coordination geometry around the Sn atom is distorted tetrahedral.
The methylation product [Cp(CO)2FeP(SeCH3)(OR)2]BF4 (R＝iPr, Et, nPr) was obtained from the reaction of (CH3)3OBF4 with organometallic species Cp(CO)2FeP(Se)(OR)2 in a molar ratio of 1:1 in CH2Cl2 at room temperature. The compounds were characterized by 1H, 31P, 77Se NMR, by FT-IR and by elemental analysis. The propyl derivative was structurally characterized. X-ray analysis reveals that the iron atom is connected to methylated-selenophosphito ligand via Fe-P bond, and one Cp ring and two CO are also coordinated to Fe atom.

並列關鍵字

Methylation ； Iron complex ； Tin complex ； Mercury complex ； dialkyl diselenophosphate ligand

參考文獻

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