丙烯睛五氨(II)(III)錯合物之熱力學與動力學研究

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Title:	丙烯睛五氨(II)(III)錯合物之熱力學與動力學研究
Other Titles:	Thermodynamic and Kinetic studies of allylcyanide pentaammineruthenium(II,III)
Authors:	許桂爾 Hsu, Guey-Er
Contributors:	葉玉堂 Andrew Yeh 東海大學應用化學系
Keywords:	結合異構;水解
Date:	1997
Issue Date:	2011-05-25T08:59:26Z (UTC)
Abstract:	Ru(NH3)5NCCH=CH2(II)錯合物，以一當量氧化的結果為氧化伴隨配位基水解反應，而在Ru(NH3)5NCCH2CH=CH2(II)錯合物，同樣以一當量氧化的結果和一般具CN配位基一樣，同樣具有配位基水解現象發生，在UV、 CV 的結果可得到印證，不同的是在UV的觀察中氧化的結果另有一吸收在508 nm，經由熱力學與動力學的探討，並配合單離產物的結果顯示，氧化的結果有兩種產物，一為水解反應，產物為 (NH3)5RuNHC(=O)CH2CH=CH2(II) 最大吸收波長為372nm，其吸光係數為1731 (1/Mcm)。另一為結合異構化反應，產物為(NH3)5RuCH(CN)CH=CH2(II) 最大吸收波長為508 nm ，其吸光係數為6231 (1/Mcm)。 The oxidation of Ru(NH3)5NC-CH=CH2(II) complexes by one quivalent of S2O8(-2) is accompairied by the hydrolysis reaction of the ligand with Ru(NH3)5NHCOCH=CH2(II) as the final product .when the ligand is hanged to NC-CH-CH2=CH2 , a linkage isomerization from -CN bound to -CH2-bound occurs in addition to the hydrolysis of the ligand when thecomplex is oxidized to Ru( III). The linkage isomerization product (NH3)5RuCH(CN)CH=CH2(II) (A) exhibits an intense LMCT absorption at 508 nm (oefficient of absorptionc is 6231 (1/M*cm) ) . The irreversibility ofthe cyclic Voltammogram of A indicates that the complex is unstable and aquates upon reaction . Both ligand hydrolysis and linkage isomerization reactions of Ru(NH3)5NC-CH2-CH=CH2(III) complex are base catalyzed and the mechanism of the reactions are investigated by the kinetic study .
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