| Abstract: | 經由(a) 2,2'-diselanediylbis(4-methylbenzenethiol) 配位基與 [Mn(CO)5]- 進行氧化加成及去 CO 反應；(b) 3,4-toluenedithiol 配位基與[Mn(CO)5]- 的氧化加成及去CO反應；(c) Mn2(CO)6(?-?4-SC6H3(CH3)E-EC6H3(CH3)S) (E = Se(3)；E = S (4))與[BH4]- 的反應，合成出五配位、十六電子的金屬化合物 [Mn(CO)3(E,S-C6H3-CH3)]- (E = Se(1)；E = S (2))，經由單晶 X-ray 繞射解析後，顯示 complexes 1、2 的結構接近四角錐體。complexes 1、2 的 1H NMR 光譜顯示出苯環上甲基的質子， 1H NMR (CDCl3)：δ2.271(s) ppm (E = Se) ，2.295(s) ppm (E = S)。由此五配位電子不飽和化合物的 IR ν(CO)光譜與之前文獻的記載，排列出此類 bidentate ligands π-donating 能力強弱次序為：[TeC6H4-o-NH]2- > [SeC6H4-o-NH]2- > [SC6H4-o-NH]2- > [S,Se-C6H3-CH3]2- > [S,S-C6H3-CH3]2- > [SC6H4-o-S]2- > [SC6H4-o-O]2- > [OC6H4-o-O]2-。再同樣為 Group 6 的 Re 之 carbonyls 化合物與配位基 [K]2[E,S-C6H3-CH3] (E = Se，S) 反應得到 complexes 7、8 ，並根據之前文獻中[(CO)3Mn(?-SC8N2H4-o-S-)]22-之合成，推測 complexes 7、8 可能是由兩分子的五配位、十六電子 [Re(CO)3(E,S-C6H3-CH3)]- (E = Se (15)；E = S (16)) 所配位鍵結形成，而先合成出 Re2(CO)6(?-?4-SC6H3(CH3)E-EC6H3(CH3)S) (E = Se(9)；E = S (10))，再與 [BH4]- 反應得到complexes 7、8，更提高了此一說法的可能性。為了明確了解五配位、十六電子化合物的合成途徑，故分別對complexes 1、2、7、8 做了對 CO 氣體的反應性實驗及 protonation 反應。與 CO 氣體的反應得到了 cis-[PPN][(CO)4M(S,E-C6H3-CH3)] (M = Mn、E = Se(5)；M = Mn、E = S(6)；M = Re、E = Se(11)；M = Re、E = S(12))，而 complexes 11、12 已成功得到晶體，並以單晶 X-ray 繞射解析得到晶體結構，由於 complexes 5、6、11、12 其 CO 十分容易脫去，目前僅能成功得到 complexes 11、12 晶體。而 protonation 反應確定皆可得到中性的雙核化合物M2(CO)6(?-?4-SC6H3(CH3)E-EC6H3(CH3)S) (M = Mn，E = Se(3)；M = Mn，E = S(4)；M = Re，E = Se(9)；M = Re，E = S(10))，且皆已成功得到晶體 並進行單晶 X-ray 繞射解析，而complexes 4、10 在先前文獻中已用別種方法合成出來，在此是以不同方法合成，亦能證明其它路徑的可行性。
The sixteen-electron five-coordinate metal complexes [Mn(CO)3(E,S-C6H3-CH3)]- (E = Se(1)；E = S (2)) were synthesized by (a) the oxidative decarbonylation addition of 2,2'-diselanediylbis(4-methylbenzenethiol) and [Mn(CO)5]- ; (b) the oxidative decarbonylation addition of 3,4-toluenedithiol and [Mn(CO)5]- ; (c) the reaction of Mn2(CO)6(?-?4-SC6H3(CH3)E-EC6H3(CH3)S) (E = Se(3)；E = S (4)) and [BH4]-. Based on the single crystal X-ray structure analyses, the crystal structures of complexes 1 and 2 show square pyramidal structure. The protons of methyl group were identified by 1H NMR spectroscopy( 1H NMR (CDCl3)：δ2.271(s) ppm (E = Se),2.295(s) ppm (E = S)). The protons of methyl group of complexes 1 and 2 were identified by 1H NMR spectroscopy, (1H NMR (CDCl3)：δ2.271(s) ppm (E = Se),2.295(s) ppm (E = S)).The comparisons of IR v(CO) data of 1,2 and previously reported complexes revealed that the π- donating ability of the bidentate ligand was demonstrated in the order of [TeC6H4-o-NH]2- > [SeC6H4-o-NH]2- > [SC6H4-o-NH]2- > [S,Se-C6H3-CH3]2- > [S,S-C6H3-CH3]2- > [SC6H4-o-S]2- > [SC6H4-o-O]2- > [OC6H4-o-O]2-. Complexes 7 and 8 were obtained by the reaction of Re carbonyl complexes with [K]2[E,S-C6H3-CH3] (E = Se，S). Accroding to previous study, complexes 7 and 8 may be afforded via the combination of two mononuclear [Re(CO)3(E,S-C6H3-CH3)]- (E = Se (15)；E = S (16)). Alternatively, complexes 7 and 8 could be synthesized by reation of complexes 9 and 10 with [BH4]- ,respectively. In order to study the reactivity of the sixteen-electron five-coordinate metal complexes, the purge of CO and protonation reaction were conducted with complexes 1, 2, 7 and 8, respectively. The structures of cis-[PPN][(CO)4Re(S,E-C6H3-CH3)] (E = Se(11)； E = S(12)) successfully identified by single crystal X-ray diffration. However, the crystallizations of cis-[PPN] [(CO)4Mn(S,E-C6H3-CH3)] (E = Se(5)；E = S(6)) were unsuccessful because of the lability of the carbonyl group in cis-[PPN][(CO)4Mn(S,E-C6H3-CH3)] (E = Se(5)；E = S(6)). The neutral compound M2(CO)6(?-?4-SC6H3(CH3)E-EC6H3(CH3)S) (M = Mn，E = Se(3)；M = Mn，E = S(4)；M = Re，E = Se(9)；M = Re，E = S(10)) were acquired and identified by single crystal X-ray diffration.In addition, the protonation of complexes 1, 2, 7 and 8 with HBF4?OEt2 yielded the neutral dimeric complexes 3, 4, 9 and 10 with S-S, Se-Se bond, respectively. |
