十六電子、五配位錳/錸-硫、硒化合物之合成與反應性探討

Synthesis and Reactivity of the Sixteen-Electron、Five-coordinate Manganese / Rhenium - Chalcogenolate Complexes

洪士軒(Shih Hsuan Hung)

指導教授 ： 陳建宏

中山醫學大學/醫學院/醫學研究所/碩士(2009年)

https://doi.org/10.6834/CSMU.2009.00012

摘要

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(µ-ŋ4-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(µ-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(µ-ŋ4-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(µ-ŋ4-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。

關鍵字

十六電子 ； 五配位 ； 錳 ； 錸

並列摘要

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(µ-ŋ4-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(µ-ŋ4-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.

並列關鍵字

Sixteen-Electron ； Five-coordinate ； Manganese ； Rhenium

參考文獻

3. Pertutz, R. N；Turner, J. J. J. Am. Chem. Soc. 1975, 97, 4791.

1. Liaw, W.-F.； Lee, C.-M.；Horng, L.；Lee, G.-H.；Peng, S.-M. Organometallics 1999, 18, 782.

2. Miessler, G. L.；Tarr , D. A. Inorganic Chemistry 3rd Edition 2004 by Pearson Education, Inc.

4. (a). Sellmann, D.；Schwarz, J. J. Organomet. Chem. 1983, 241,243. (b). Sellmann, D.；Luwig, W. J. Organomet. Chem. 1984,269, 171. (c). Sellmann, D.；Luwig, W.；Huttner, G.；Zsolnai, L. J. Organomet. Chem. 1985, 294, 199. (d). Sellmann, D.；Wille, M.；Knoch, F. Inorg. Chem. 1993, 32, 2534.

5. Frantisek Hart1；Antonin V. Jr.；Lynn A. deLearie,f；Cortlandt G. Pierpont Inorg. Chem. 1990, 29, 2073.