Abstract
以丁二酮[2,3]]□及二胺基化合物為起始物，利用兩種不同之方法合成一系列之二亞胺基二 化合物，3,8- 二甲基-4,7- 二氮-3,7- 癸碳二烯-2,9- 二酮二□，3,9-二甲基-4,8-二氮-3.8- 十一碳二烯-2,10- 二酮二□，3,6,6,9-四甲基-4,8- 二氮-3,8-十二碳二 烯-2,10- 二酮二□，3,10-二甲基-4,9-二氮-3,9- 十二碳二烯-2,11 二酮二□及苯基[5,6]-3,8-二甲基-4,7- 二氮-3,7- 癸碳二烯-2,9- 二酮二□，以及以2-氮-2-甲基-3- 亞硝基丁烷，再與不同種類之二胺基化合物反應合成一系列之二胺基二□化合物，3,3,8,8- 四甲基-4,7- 二氮癸烷-2,9- 二酮二□，3,3,9,9-四甲基-4,8- 二氮十一烷-2,10- 二酮二□，3,3,6,6,9,9-六甲基-4,8- 二氮十一烷-2,10-二酮二□，3,6,6,9- 四甲基-4,8- 二氮十一烷-2,10-二酮二□及3,3,10,10-四甲基-4,9- 二氮十二烷-2,11- 二酮二□，這些化合物並分別經由紅外光譜，質譜，元素分析，熔點，核磁共振光譜及X-射線繞射分析法鑑定。且這些合化物分別與銅（Ⅱ）及鎳（Ⅱ）金屬鹽類反應所得之錯合物晶體，可利用X-射線繞射分析法得到其結構圖。金屬錯化合物之硫氰化物會有接合異構物產生，其一般之化學式為（圖表省略）及（圖表省略）等七種配位子，皆已合成及定性，利用紅外光譜及X-射線繞射分析鑑定鍵結型式為Cu-SCN或Cu-SCN，並討論鍵結型式與錯化合物配位之四牙配位子結構之相依性。在溫度25℃和離子強度為0.10M NAC104時，經由電位滴定法可得到（圖表省略）及d,1-HM-PAO等10種配位子的質子化常數，同時亦可以測得這些配位子的二價銅及鎳錯化合物之穩定常數並加以討論之。在溫度25℃和離子強度為（圖青省略）時，經由卡計測量法可得到二亞胺基二□配位子質子化的熱量變化，並用來計算質子化的熵變化。所測得之值可與配位子的質子化常數作比較。在相同之條件下，亦可求這些配位子與銅（Ⅱ）及鎳（Ⅱ）形成錯化合物之熱焓量之變化，並計算錯化合物形成的熵變化。結果發現含5-6-5 圓環的二亞胺基二★錯化合物比5-7-5 ，5-5-5 圓環錯化合物穩定，這較大的穩定度主要歸因於反應時放出較多的熱量利用截止流動法研究二胺基二★銅（Ⅱ）錯化合物形成反應之動力學，並探討其反應可能之途徑，提出其形成反應機構，二價銅離子與未質子化配位形成反應中，第一個金屬－氮鍵的形成為速率決定步驟；至於二價的銅離子與單質子化配位子之形成反應中，其質子的失去則為速率限制步驟。在溫度25℃（圖表省略）和離子強度為（圖表省略）時，利用截止流動法研究這些配位子銅（Ⅱ）錯化合物的酸解離反應，這些反應為特殊酸催化，不過其反應速率常數不受醋酸，氯化醋酸和二氯醋酸濃度的影響。並探討配位子的立體效應，圍帶張力及配位子鹼度對錯化合物解離速率之影響，發現5-5-5,5-7-5 圓環錯化合物之解離速率常數較5-6-5 圓環大很多。///////The diazadioxime ligands, 3,8-dimethyl-4,7-diaza-3,7-decadiene-2,9-dionedioxime, 3,9-dimethyl-4,8-diaza-3,8-undecadiene-2,10-dione dioxime,3,6,6,9-tetramethyl-4,8-undecadiene-2,10-dionedioxime,3,10-dimethyl-4,9-diaza-3,9-dodecadiene-2, 11-dionedioxime, benzo [5,6]-3,8- dimethyl-4,7-diaza-3,7--diaza-3,7-decadiene-2,9-dione dioxime,3,3,8,8-tetramethyl-4,7-diazadecane-2,9-dione dioxime,3,3,9,9-tetramethyl-4,8-diazaundecane-2,10-dione dioxime,3,3,6,6,9,9-hexamethyl-4,8-diazaundecane-2,10-dione dioxime,3,6,6,9-tetramethyl-4,8-diazaundecane-2,10-dione dioxime,3,3,10,10-tetramethyl-4,9-diazadodeca-ne-2,11-dione dioxime, weresynthesized. Their copper [Ⅱ] and nickel [Ⅱ] complexes were preparedfrom these ligands and metal salts. The crystal structures of some ofthese metal complexes were obtained by the X-ray diffraction method.The protonation constants of these ligands were determinedpotentiometrically in O.10 M NaC104 at 25.0℃. The formation of copper[Ⅱ] and nickel [Ⅱ] complexes of these ligands were investigatesquantitatively by potentiometric techniques under the same conditions.Electronic spectra of the nickel [Ⅱ] and copper [Ⅱ] complexes of theseligands and their deprotonated species formed in aqueous solution weremeasured.Complexes of general formula（圖表省略）Where（圖表省略）EnAO, PnAO and meso-HM-PAO, have been prepared and characterized. Theirinfrared spectra were used to establish the bond type Cu-SCN or Cu-NCS.The formation kinetics of diamino dioxime copper [Ⅱ] complexes have beenstudied using stopped-flow techniques. Two possible pathways for thecomplexation reactions of copper [Ⅱ] ion with these ligands arediscussed. The first metal-nitrogen bond formation is proposed as therate-determining step for the reactions of copper [Ⅱ] ion with theunprotonated ligands; proton loss is the rate-limiting step in thereactions of copper [Ⅱ] ion with the monoprotonated ligands.The dissociation kinetics of the copper [Ⅱ] complexes of these ligandshave been studied at 25,0℃ and u=5.0 M（圖表省略）by the stopped-flow method and spectroscopic technique. These reactionsare specific-acid catalyzed, however, the rate constants of thesereactions do not depend on the concentrations of acetic, monochloroacetic, and dichloroacetic acids. At pH values below 1.0 both theproton-assisted and the direct proton-ation pathways make contributions tothe rates. The values of（圖表省略）and （圖表省略）increase in the order Cu（圖表省略）This sequence is not the same with the order of the stability constant ofthese complexes. Although（圖表省略）is more stable than Cu（圖表省略）,it dissolves faster than Cu（圖表省略）The main reasonance is steric effect. The Cu-N bond distances ofCu（圖表省略）and（圖表省略）do not differ significantly, nor. do the（圖表省略）and（圖表省略）of these two complexss.