臺灣博碩士論文加值系統

為了獲致在醫藥或材料工業上具有應用價值之希夫鹼(Schiff base)配位體與相對應之金屬錯合物，本研究致力於柳醛類 苯甲醯腙配位體及其過渡金屬錯合物之合成並應用於偶聯反應之催化活性。首先合成十五種不同取代基柳醛 苯甲醯腙配位體，在三乙胺的存在下，分別與雙(三苯基膦)氯化鎳進行錯合反應，而獲得相對應之鎳金屬錯合物；又各種柳醛 苯甲醯腙配位體在三乙胺的存在下，分別與三聚醋酸鈀搭配三苯基膦進行錯合反應，而獲得相對應之鈀金屬錯合物。並進行鎳、鈀金屬錯合物之光譜分析及鑑定結構。再利用0.1 mol %的鈀或鎳金屬錯合物催化鈴木反應與赫克反應，藉由NMR光譜可獲得偶聯產物之產率，結果顯示鈀金屬錯合物比鎳金屬錯合物更加具有催化效果；鈀金屬錯合物的催化活性優於其在合成過程所使用的醋酸鈀原料。因此，本研究所合成之鈀金屬錯合物在化學工業上，是具有相當應用價值的催化劑。

With the purpose of obtaining useful Schiff base ligands and the corresponding metal complexes in medical field or material industry, this study aimed at syntheses of various substituted-salicylaldehyde benzoylhydrazones and the corresponding transition metal complexes. In addition, the synthesized metal complexes were applied to cross-coupling reaction for evaluating catalytic activity. The fifteen kinds of substituted-salicylaldehyde benzoylhydrazones were treated with dichloride bis(triphenylphosphine)nickel to give nickel complexes in the presence of triethylamine. Palladium complexes were synthesized by the reaction of palladium acetate with the corresponding Schiff base ligands and triphenylphosphine in the presence of triethylamine. Furthermore, structure of nickel complexes and palladium complexes were identified and discussed by spectral analysis. Catalytic activity of palladium complexes and nickel complexes were tested toward the Suzuki reaction and Heck reaction with 0.1 mol % loading under optimized conditions to afford NMR yield of the coupled products. The results showed that the catalytic activity of palladium complexes was better than nickel complexes and palladium acetate. Therefore, the synthesized palladium complexes are very valuable catalysts in chemical industry.

謝誌................................................................................................I
中文摘要.........................................................................................Ⅱ
英文摘要........................................................................................Ⅲ
目錄...............................................................................................Ⅳ
圖目錄............................................................................................Ⅴ
表目錄...........................................................................................Ⅵ

第一章 各種柳醛類 苯甲醯腙配位體之合成研究
一、前言.........................................................................................1
二、結果與討論..............................................................................4
三、實驗部分..................................................................................8
第二章 各種柳醛類 苯甲醯腙鎳過渡金屬錯合物之合成研究
一、前言.......................................................................................21
二、結果與討論.............................................................................28
三、實驗部分................................................................................39
第三章 各種柳醛類 苯甲醯腙鈀過渡金屬錯合物之合成研究
一、前言.......................................................................................56
二、結果與討論.............................................................................60
三、實驗部分.................................................................................66
第四章 鎳、鈀金屬錯合物在偶聯反應中催化活性之應用
一、前言......................................................................................81
二、結果與討論..........................................................................83
三、實驗部分..............................................................................94
第五章 結論.................................................................................100
參考文獻.....................................................................................101

1. 鄭建中，“淺談生物無機”，中央研究院化學研究所，自然科學簡訊第十二卷第二期，62-65頁，2000。
2.Mohamed, G. G.; Mahmoud, W. H.; Diab, M. A.; El-Sonbati, A. Z.; Abbas, S. Y. “Synthesis, characterization, theoretical study and biological activity of Schiff base nanomaterial analogues” J. Mol. Struct. 2019, 1181, 645-659.
3.Mondal, S.; Mondal, T. K.; Rajesh, Y.; Mandal, M.; Sinha, C. “Copper(II)-Sulfonamide Schiff base complexes: Structure, biological activity and theoretical interpretation” Polyhedron 2018, 151, 344-354.
4.Pervaiz, M.; Yousaf, M.; Ahmad, I.; Munawar, A.; Saeed, Z.; Adnan, A.; Gulzar, T.; Kirn, S.; Kamal, T.; Ahmad, A. “Synthesis, spectral and antimicrobial studies of amino acid derivative Schiff base metal (Co, Mn, Cu, and Cd) complexes” Spectrochim. Aata A 2019, 206, 642-649.
5.Rodriguez-Arguelles, M. C.; Ferrari, M. B.; Bisceglie, F.; Pelizzi, C.; Pelosi, G.; Pinelli, S.; Sassi, M. “Synthesis, characterization and biological activity of Ni, Cu and Zn complexes of isatin hydrazones” J. Inorg. Biochem. 2004, 98, 313-321.
6.Kaczmarek, M. T.; Jastrzab, R.; Hołderna-Kedzia, E.; Radecka-Paryzek, W. “Self-assembled synthesis, characterization and antimicrobial activity of zinc(II) salicylaldimine complexes” Inorg.Chim. Acta 2009, 362, 3127-3133.
7.Sennappan, M.; Krishna, P. M.; Hosamani, A. A.; Krishna, R. H. “Synthesis, characterization, nucleic acids interactions and photoluminescent properties of methaniminium hydrazone Schiff base and its Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes” J. Mol. Struct. 2018, 1164, 271-279.
8.Despaigne, A. A. R.; Silva, J. G. D.; Carmo, A. C. M.; Piro, O. E.; Castellano, E. E.; Beraldo, H. “Structural studies on zinc(II) complexes with 2-benzoylpyridine-derived hydrazones” J. Inorg. Biochem. 2009, 362, 2117-2122.
9.Backes, G. L.; Neumann, D. M.; Jursic, B. S. “Synthesis and antifungal activity of substituted salicylaldehyde hydrazones, hydrazides and sulfohydrazides” Bioorgan. Med. Chem. 2014, 22, 4629-4636.
10.Avaji, P. G.; Kumar, C. H. V,; Patil, S. A.; Shivananda, K. N.; Nagaraju, C. “Synthesis, spectral characterization, in-vitro microbiological evaluation and cytotoxic activities of novel macrocyclic bis hydrazone” Eur. J. Med. Chem. 2009, 44, 3552-3559.
11.Shih, M. H.; Chen, J. C.; Ling, G. L.; Lin, Z. T.; Sun, M. H. J. “Novel synthesis of palladium(II) complexes derived from 3-arylsydnone-4-carbaldehyde N(4)-phenylthiosemicarbazones and biological activity” Pharm. Pharmacol. 2014, 66, 73-83.
12.施美秀、呂嘉霖，2017，“雙硫半卡腙配位體及其合成方法”，中華民國發明專利證書I649300號。
13.呂嘉霖，“合成新型脂肪族1,2-二酮類 雙硫半卡腙配位體及其過渡金屬錯合物並探討其抗氧化活性”，南臺科技大學 化材系，碩士論文，2017。
14.Cao, W.; Liu, Y; Zhang, T; Jia, J. “Synthesis, characterization, theoretical and antimicrobial studies of tridentate hydrazone metal complexes of Zn(II), Cd(II), Cu(II) and Co(III)” Polyhedron 2018, 147, 62-68.
15.Pereira, E.; Gomes, L.; Castro, B. “Synthesis, spectroscopic and electrochemical study of nickel(II) complexes with tetradentate asymmetric Schiff bases derived from salicylaldehyde and methyl-2-amino-1-cyclopentenedithiocarboxylate” Inorg. Chem. Acta 1998, 271, 83-92.
16.Arshad, N.; Yunus, U.; Razzque, S.; Khan, M.; Saleem, S.; Mirza, B.; Rashid, N. “Electrochemical and spectroscopic investigations of isoniazide and its analogs with ds. DNA at physiological pH: Evaluation of biological activities” Eur. J. Med. Chem. 2012, 47, 452-461.
17.Mohanraj, M.; Ayyannan, G.; Raja, G.; Jayabalakrishnan, C. “Evaluation of DNA binding, DNA cleavage, protein binding, radical scavenging and in vitro cytotoxic activities of ruthenium(II) complexes containing 2,4-dihydroxy benzylidene ligands” Mater. Sci. Eng. C. 2016, 69, 1297-1306.
18.Avaji, P. G.; Kumar, C. H. V.; Patil, S. A.; Shivananda, K. N.; Nagaraju, C. “Synthesis, spectral characterization, in-vitro microbiological evaluation and cytotoxic activities of novel macrocyclic bis hydrazone” Eur. J. Med. Chem. 2009, 44, 3552-3559.
19.Singh, V. P.; Singh, P. “Synthesis, spectral characterization and thermal studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes with 2-amino benzoic acid and 2-hydroxy benzoic acid thiophen-2-ylmethylene hydrazide” J. Mol. Struct. 2013, 1035, 363-370.
20.Wang, C.; Xing, N.; Feng, W.; Guo, S.; Liu, M.; Xu, Y.; You, Z. “New mononuclear dioxidomolybdenum(VI) complexes with hydrazone ligands: synthesis, crystal structures and catalytic performance” Inorg. Chim. Acta 2019, 486, 625-635.
21.Asha, T. M.; Kurup, M. R. P. “Synthesis, spectroscopy, electrochemistry, crystal structures and in vitro cytotoxicity of mononuclear molybdenum(VI) complexes incorporating tridentate ONO donor aroylhydrazone with auxiliary coordination site” Inorg. Chim. Acta 2018, 483, 44-52.
22.Chena, Y. L. ; Konga, X.; Xieb, Y.; Hidera, R. C. “The interaction of pyridoxal isonicotinoyl hydrazone (PIH) and salicylaldehyde isonicotinoyl hydrazone (SIH) with iron” J. Inorg. Biochem. 2018, 180, 194-203.
23.Palepu, N. R.; Premkumar, J. R.; Verma, A. K.; Bhattacharjee, K.; Joshi, S. R.; Forbes, S.; Mozharivskyj, Y.; Rao, K. M. “Antibacterial, in vitro antitumor activity and structural studies of rhodium and iridium complexes featuring the two positional isomers of pyridine carbaldehyde picolinic hydrazone ligand” Arab. J. Chem. 2018, 11, 714-728.
24.Sutradhar, M.; Rajeshwari, Barman, T. R.; Fernandes, A. R.; Paradinha, F.; Roma-Rodrigues, C.; Silva, M. F. C. G.; Pombeiro, A. J. L. “Mixed ligand aroylhydrazone and N-donor heterocyclic Lewis base Cu(II) complexes as potential antiproliferative agents” J. Inorg. Biochem. 2017, 175, 267-275.
25.Backes, G. L.; Neumann, D. M.; Jursic, B. S. “Synthesis and antifungal activity of substituted salicylaldehyde hydrazones, hydrazides and sulfohydrazides” Bioorg. Med. Chem. 2014, 22, 4629-4636.
26.Carcelli, M.; P.Mazza, Pelizzi, C.; Zani, F. “Antimicrobial and genotoxic activity of 2,6-diacetylpyridine bis(acylhydrazones) and their complexes with some first transition series metal ions. X-ray crystal structure of a dinuclear copper(II) complex” J. Inorg. Biochem. 1995, 57, 43-62.
27.Singh, V. P.; Singh, S.; Singh, D. P. “Synthesis, characterization and biocidal activity of some transition metal(II) complexes with isatin salicylaldehyde acyldihydrazones” J. Enzym. Inhib. Med. Ch. 2011, 27, 319-329.
28.Macková, E.; Hrušková, K.; Bendová, P.; Vávrová, A.; Jansová, H.; Hašková, P.; Kovarˇíková, P.; Vávrová, K.; Šimunek, T. “Methyl and ethyl ketone analogs of salicylaldehyde isonicotinoyl hydrazone: Novel iron chelators with selective antiproliferative action” Chem.-Biol. Interact. 2012, 197, 69-79.
29.Prabhu, R. N.; Ramesh, R. “Catalytic application of dinuclear palladium(II) bis(thiosemicarbazone) complex in the Mizoroki-Heck reaction” Tetrahedron Lett. 2012, 53, 5961-5965.
30.Suganthy, P. K.; Prabhu, R. N.; Sreedevi, V. S. “Nickel(II) thiosemicarbazone complex catalyzed Mizoroki-Heck reaction” Tetrahedron Lett. 2013, 54, 5695-5698.
31.楊育陞，“各取代基柳醛類 硫半卡腙及混合三苯膦多樣化配位體之過渡金屬錯合物合成”，南臺科技大學 化材系，碩士論文，2014。
32.Shih, M. H.; Xu, Y. Y.; Yang, Y. S.; Lin, T. T. “Syntheses of nickel(II) complexes from novel semicarbazone ligands with chloroformylarylhydrazine, benzimidazole and salicylaldehyde moieties” Molecules 2015, 20, 5184-5201.
33.Prabhu, R. N.; Ramesh, R. “Synthesis, structural characterization, electrochemistry and catalytic transfer hydrogenation of ruthenium(II) carbonyl complexes containing tridentate benzoylhydrazone ligands” J. Organomet.Chem. 2012, 718, 43-51.
34.Suganthy, P. K.; Prabhu, R. N.; Sridevi, V. S. “Synthesis, structure and catalytic applications of octahedral nickel(II) benzoylhydrazone complex: Suzuki-Miyaura cross-coupling reaction of aryl bromides with arylboronic acid” Inorg. Chim. Acta 2016, 449, 127-132.
35.Mishra, M; Tiwari, K.; Shukla, S.; Mishra, R.; Singh, V. P. “Synthesis, structural investigation, DNA and protein binding study of some 3d-metal complexes with N’-(phenyl-pyridin-2-yl-methylene)-thiophene-2-carboxylic acid hydrazide” Spectrochim. Acta 2014, 132, 452-464.
36.Kumar, S.; Nath, M. “New diorganotin(IV) complexes of salicylaldehyde based hydrazones bearing furan heterocycle moiety: X-ray structural investigation of dimethyltin(IV) and diphenyltin(IV) complexes” J. Organomet.Chem. 2018, 856, 87-99.
37.Azarkish, M.; Akbari,A.; Sedaghat,T.; Simpson, J. “Ternary complexes of Zn(II) and Cu(II) with 1-((2-hydroxynaphthalen-1-yl)methylene)-4-phenythiosemlicar- bazidein the presence of heterocyclic bases as auxiliary ligands: Synthesis, spectroscopic and structural characterization and antibacterial activity” J. Mol. Struct. 2018, 1156, 34-42.
38.Kuchtanin, V.; Klescíková, L.; Soral, M.; Fischer, R.; Ruzicková, Z.; Rakovsky´, E.; Moncol, J.; Segla, P. “Nickel(II) Schiff base complexes: Synthesis, characterization and catalytic activity in Kumada–Corriu cross-coupling reactions” Polyhedron 2016, 117, 90-96.
39.Rosenberg, B; Van Camp, L; Krigas, T. “Inhibition of cell division in escherichia coli by electrolysis products from a platinum electrode” Nature, 1965, 205, 698-699.
40.Gao, E. J.; Wang, K. H.; Zhu, M. C. “Hairpin-shaped tetranuclear palladium(II) complex: Synthesis, crystal structure, DNA binding and cytotoxicity activity studies” Eur. J. Med. Chem. 2010, 45, 2784-2790.
41.Hecht, S. M. “Bleomycin: New perspectives on the mechanism of action” J. Nat. Prod. 2000, 63, 158-168.
42.Gao, E.; Liu, C.; Zhu, M. Lin, H. Wu, Q. Liu, L. “Current development of Pd(II) complexes as potential antitumor agents” Anti-Cancer Agents Med. Chem. 2009, 9, 356- 368.
43.Abu-Surrah, A. S.; Al-Sadoni, H. H.; Abdalla, M. Y. “Palladium-based chemotherapeutic agents: Routes toward complexes with good antitumor activity” Cancer. Ther. 2008, 6, 1-10.
44.Singh, V. P.; Singh, P.; Singh, A. K. “Synthesis, structural and corrosion inhibition studies on cobalt(II), nickel(II), copper(II) and zinc(II) complexes with 2-acetylthiophene benzoylhydrazone” Inorg. Chim. Acta 2011, 379, 56-63.
45.Ramachandran, E.; Senthil Raja, D.; Nigam. Rath, P. Natarajan, K. “Role of substitution at terminal nitrogen of 2-oxo-1,2-dihydroquinoline-3-carbaldehyde thiosemicarbazones on the coordination behavior and structure and biological properties of their palladium(II) complexes” Inorg. Chem. 2013, 52, 1504-1514.
46.Song, H.; Chen, D.; Pi, C.; Cui, X.; Wu, Y. “Palladium(II)-catalyzed direct regioselectively oxidative acylation of azobenzenes with toluene derivatives” J. Org. Chem. 2014, 79, 2955-2962.
47.Drout, R. J.; Robison, L.; Farha, O. K. “Catalytic applications of enzymes encapsulated in metal–organic frameworks” Coordin. Chem. Rev. 2019, 381, 151-160.
48.蔡蘊明，“2010諾貝爾化學獎簡介”，臺灣大學 化學系，2010。
49.Kumar, A.; Agarwal, M.; Singh, A. K. “Schiff bases of 1’-hydroxy-2’-acetonaphthone containing chalcogen functionalities and their complexes with and (p-cymene) Ru(II), Pd(II), Pt(II) and Hg(II): Synthesis, structures and applications in C–C coupling reactions” J. Organomet. Chem. 2008, 693, 3533-3545.
50.Shahnaz, N.; Puzari, A.; Paul, B.; Das, P. “Activation of aryl chlorides in water for Suzuki coupling with a hydrophilic salen-Pd(II) catalyst” Catal. Commun. 2016, 86, 55-58.
51.Tamizh, M. M.; Cooper, B. F. T.; Macdonald, C. L. B. Ramasamy Karvembu “Palladium(II) complexes with salicylideneimine based tridentate ligand and triphenylphosphine: Synthesis, structure and catalytic activity in Suzuki–Miyaura cross coupling reactions” Inorg. Chim. Acta 2013, 394, 391-400.
52.Khorshidifard, M.; Rudbari, H. A.; Askari, B.; Sahihi, M.; Farsani, M. F.; Jalilian, F.; Bruno, G. “Cobalt(II), copper(II), zinc(II) and palladium(II) Schiff base complexes: Synthesis, characterization and catalytic performance in selective oxidation of sulfides using hydrogen peroxide under solvent-free conditions” Polyhedron 2015, 95, 1-13.
53.Paul, P.; Butcher, R. J.; Bhattacharya, S. “Palladium complexes of 2-formylpyridine thiosemicarbazone and two related ligands: Synthesis, structure and, spectral and catalytic properties” Inorg. Chim. Acta 2015, 425, 67-75.
54.Kundu, S.; Pramanik, A. K.; Mondal, A. S.; Mondal, T. K. “Ni(II) and Pd(II) complexes with new N,O donor thiophene appended Schiff base ligand: Synthesis, electrochemistry, X-ray structure and DFT calculation” J. Mol. Struct. 2016, 1116, 1-8.
55.Sedighipoor, M.; Kianfar, A. H.; Mohammadnezhad, G.; Görls, H.; Plass, W. “Unsymmetrical palladium(II) N,N,O,O-Schiff base complexes: Efficient catalysts for Suzuki coupling reactions” Inorg. Chim. Acta 2018, 476, 20-26.
56.馬玉國，“烯烴復分解反應— 2005年諾貝爾化學獎簡介”，北京大學化學與分子工程學院，大學化學第二十一卷第一期，2006。
57.Agrahari, B.; Layek, S.; Anuradha; Ganguly, R.; Pathak, D. D. “Synthesis, crystal structures, and application of two new pincer type palladium(II)-Schiff base complexes in C-C cross-coupling reactions” Inorg. Chim. Acta 2018, 471, 345-354
58.Anuradha, S. L.; Agrahari, B.; Pathak, D. D. “Synthesis and characterization of a new Pd(II)-Schiff base complex [Pd(APD)2]: An efficient and recyclable catalyst for Heck-Mizoroki and Suzuki-Miyaura reactions” J. Organomet. Chem. 2017, 846, 105-112.
59.Kovala-Demertzi, D.; Yadav, P. N.; Demertzis, M. A.; Jasiski, J. P.; Andreadakic, F. J.; Kostas, I. D. “First use of a palladium complex with a thiosemicarbazone ligand as catalyst precursor for the Heck reaction” Tetrahedron Lett. 2004, 45, 2923-2926.