含二硒磷酸配位基之鍺、鉛金屬錯合物的合成

本次實驗利用二硒磷酸配位基NH4Se2P(OR)2（dialkyl diselenophosphate ligand）（R＝iPr, Et, nPr）與14族的金屬起始物進行反應，比較它們在光譜上與晶體結構上的差異，而所採用的金屬起始物為(C6H5)3MCl（M＝Ge, Pb）以及Pb(CH3COO)2‧3H2O。 (C6H5)3GeCl與NH4Se2P(OR)2於低溫下在diethyl ether中反應，可以獲得(C6H5)3GeSe2P(OR)2（R＝iPr, Et, nPr）；而在相同的條件下，改以(C6H5)3 PbCl也可以得到(C6H5)3PbSe2P(OR)2（R＝iPr, Et, nPr）。比較(C6H5)3GeSe2P(OR)2與(C6H5)3PbSe2P(OR)2兩者在晶體結構與NMR光譜上的差異。而將NH4Se2P(OR)2與Pb(CH3COO)2‧3H2O於室溫下以CH3OH中反應，可以獲得Pb[Se2P(OR)2]2（R＝iPr, Et, nPr），在三種衍生物當中我們得到Pb[Se2P(OiPr)2]n與Pb[Se2P(OEt)2]2兩種不同的晶體結構。而與已知的Pb[S2P(OR)2]2的結果相比較，探討Pb[Se2P(OR)2]2與Pb[S2P(OR)2]2兩者間在晶體結構與光譜上的差別。

關鍵字

鍺；亞鉛；二硒磷酸配位基；鉛

並列摘要

Complexes (C6H5)3MSe2P(OR)2 (M＝Ge, Pb；R＝iPr, Et, nPr) were prepared from the reaction of (C6H5)3MCl and NH4Se2P(OR)2 in a molar ratio of 1:1 in diethyl ether at 0 °C. The complexes were characterized by elemental analysis, 1H, 31P, 77Se NMR, positive FAB mass and X-ray. The X-ray structure consists of three phenyl rings connected to metal atom and a selenium atom from diselenophosphate ligand is also coordinated to metal atom. The other selenium atom of diselenophosphate ligand is dangling. The coordination geometry around the metal atom is distorted tetrahedral. Compounds Pb[Se2P(OR)]2 (R＝iPr, Et, nPr,) were prepared from the reaction of Pb(CH3COO)2‧3H2O and NH4Se2P(OR)2 in a molar ratio of 1:2 in methanol at room temperature. The complexes were characterized by elemental analysis, 1H, 31P, 77Se NMR, positive FAB mass and X-ray.