含二硒磷酸配位基之鈷金屬錯合物及鐵金屬磷酸鹽錯合物與汞金屬的合成反應

Cobalt complexes containing Diselenophosphate Ligands and Iron(II)-Mercury(II) Heterometallic Clusters by Selenophosphi to Groups

溫松穎(Sung-Yin Wen)

指導教授 ： 楊千金

中原大學/理學院/化學研究所/碩士(2005年)

https://doi.org/10.6840/cycu200500303

摘要

摘要
將二硒磷酸配位基NH4Se2P(OR)2（dialkyl diselenophosphate ligand）（R = iPr, Et, nPr）與Co(AcAc)3金屬起始物，在高溫迴流反應下，可以獲得Co[Se2P(OR)]3（R = iPr, Et, nPr）。利用有機配位基與無機錯合物在有機溶劑下進行自我組裝（self - assembly）， 將NH4Se2P(OiPr)2與(CH3CO2)2Co‧4H2O金屬起始物及4,4’-bipyridine (bipy)於室溫MeOH溶劑下，成功合成{CoSe2P(OiPr) 2‧(4,4’-bipyridine)}∞，為高分子鏈狀聚合物。
利用Hg(ClO4)2金屬起始物與Cp(CO)2FeP(Se)(OiPr)2 ( Cp = η5-C5H5 )，在-20°C 的丙酮下，以1 : 2及1 : 3莫耳數的比例，能夠獲得二配位與三配位 [Hg{Fe(CO)2Cp[P(Se)(OiPr)2]}n](ClO4)2（n = 2, 3）化合物。將Hg(ClO4)2金屬起始物換成HgI2，與Cp(CO)2FeP(Se)(OiPr)2在0°C 的丙酮下，以3 : 2莫耳數的比例，能夠成功合成Hg3I4(μ2-I)2{Fe(CO)2Cp[P(Se)(OR)2]}2 （R = iPr, nPr）。
這些新的錯合物結構的判定是藉由1H NMR、31P NMR、77Se NMR、FAB+ mass、elemental analysis、FT-IR 、UV-vis及X-ray 單晶繞射儀得知。

關鍵字

鐵金屬錯合物 ； 鈷金屬錯合物 ； 二硒磷酸配位基 ； 過氯酸汞 ； 碘化汞

並列摘要

Abstract
The reaction of Co(AcAc)3 with NH4SeP(OR)2 (R = iPr, Et, nPr) in a molar ratio of 1:3 in toluene at amibient temperature forms brown and red crystals of Co[Se2P(OR)]3（R = iPr, Et, nPr）.
Utilizing organic bridging ligands to connect inorganic complexes by self–assembling under organic solvents , the reaction of (CH3CO2)2Co‧4H2O、NH4Se2P(OiPr)2 and 4,4’-bipyridine in a molar ratio of 1:2:1 in MeOH at room temperature succeeded in obtaining {CoSe2P(OiPr) 2‧(4,4’-bipyridine)}∞ chain.
The two co-ordination and three co-ordination [Hg{Fe(CO)2Cp[P(Se)(OiPr)2]}n](ClO4)2（n = 2,3）Compounds are synthesized from the reaction of Hg(ClO4)2 and Cp(CO)2FeP(Se)(OiPr)2 in molar ratio of 1:2 and 1:3 in acetone at -20°C. Changing the Hg(CIO4)2 to HgI2, it can react with Cp(CO)2FeP(Se)(OR)2 in a molar ratio of 1:2:1 in acetone at low temperature to successfully form Hg3I4(μ2-I)2{Fe(CO)2Cp[P(Se)(OR)2]}2 （R = iPr, nPr）.
The structures of [Hg{Fe(CO)2Cp[P(Se)(OiPr)2]}n](ClO4)2 、Hg3I4(μ2-I)2{Fe(CO)2Cp[P(Se)(OR)2]}2（R = iPr, nPr）、Co[Se2P(OR)]3（R = iPr, Et, nPr） and {CoSe2P(OiPr) 2‧(4,4’-bipyridine)}∞ are determined and tested by the use of 1H、31P、77Se of NMR spectroscopies, FAB+ mass, FT-IR, UV-vis , single crystal X-ray crystallography and the elemental analysis.

並列關鍵字

HgClO4 ； dialkyl diselenophosphate ligand ； Co ； Mercury complex ； Cobalt complexe ； Fe ； Iron complex ； HgI2

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