有机镍化学

有機鎳化學是一門研究含有-化學鍵的化合物(有機鎳化合物)的理化性質、合成與反應的學科,是有機金屬化學的分支[1][2]四羰基鎳是第一個被人類合成的有機鎳化合物,被化學家路德維希·蒙德在1890年首度合成。它立刻被用於蒙德法來提煉鎳金屬。隨後有機鎳化合物用於不同過渡金屬催化反應催化劑

organonickel
organonickel

分類與合成

在鎳化合物中,鎳的氧化數多爲0或者+2。有很多鎳的烷基或芳基配合物的化學式都是NiR(X)L2。而NiR2類的鎳配合物有時只有12個價電子,而他們會透過溶劑化來增加自己的價電子數,穩定自己。

而鎳的烯烴配合物較爲常見。例如具備兩個環辛二烯配體雙(1,5-環辛二烯)鎳,它是一個18電子的配合物,其中有去10個電子由鎳提供,而剩餘的4×2個電子有配體的雙鍵提供。它對空氣極爲敏感[3],可溶於有機溶劑[4][5]。鎳的烯烴配合物有較多實際的用途,例如可以用於壳牌高级烯烃过程英语Shell Higher Olefin Process[6]等烯烴的聚合反應中。

烯丙基型鹵代烴可以與四羰基鎳反應生成(烯丙基)2Ni2Cl 2[7]。它是一種π-烯丙基配合物,鎳的氧化數為+2,是烯丙基親核試劑的來源。

鎳亦可以跟卡賓生成配合物,其中包含碳-鎳雙鍵: [8]

Nickel carbenes

是一個常用的試劑[9]

反應

烯烴或炔烴的低聚

鎳化合物可以催化烯烴或炔烴的低聚。例如在氰化鎳的存在下,乙炔四聚成環辛四烯[10]

Reppe's synthesis of cyclooctatetraene

溴化鎳、鋅可以成爲 [2+2+2]環加成反應的催化劑,反應涉及到苯炔[11]可以把二價鎳還原成零價鎳。

Alkyne trimerization involving an aryne

在這些實驗中,鎳配合物的存在可能不太明顯,但如果細心地設計實驗,鎳配合物中間體便可以定量生成[12][13]

Reaction of N-(benzenesulfonyl)benzaldimine with two equivalents of diphenylacetylene

偶聯反應

鎳配合物可以催化烯丙基或芳基鹵代烴的偶聯反應

Coupling of 3-Chloro-2-methyl-1-propene to 2,5-dimethyl-1,6-hexadiene

而催化量的鎳化合物亦可用於熊田偶聯反應[14],機理跟其他很多金屬催化的反應一樣,經歷氧化加成轉金屬化順反異構化還原消去幾部分:

Kumada偶联反应机理
Kumada偶联反应机理

鎳化合物亦可用於根岸偶聯反應,其中有機鋅試劑鹵代烴在鎳配合物的催化下發生偶聯,生成一個新的C-C鍵[15][16]

羰基化

鎳催化烯烴和炔烴的羰基化反應丙烯酸的工業合成曾經用到溴化鎳鹵化銅作爲催化劑:

Nickel catalyzed carbonylation of acetylene to acrylic acid

參見

參考資料

  1. ^ F.A. Carey R.J. Sundberg Advanced Organic Chemistry 2nd Ed. ISBN 0-306-41199-7
  2. ^ Comprehensive organometallic chemistry III Robert Crabtree, Mike Mingos 2006 ISBN 0-08-044590-X
  3. ^ Wilke, G. Contributions to Organo-Nickel Chemistry. Angewandte Chemie International Edition. 1988, 27 (1): 185–206. doi:10.1002/anie.198801851. 
  4. ^ Schunn, R. A.; Ittel, S. D.; Cushing, M. A. Bis(1,5-Cyclooctadiene)Nickel(0) 28. 1990: 94–98. ISBN 978-0-470-13259-3. doi:10.1002/9780470132593.ch25.  |journal=被忽略 (帮助)
  5. ^ Wender, Paul A.; Smith, Thomas E.; Duong, Hung A.; Louie, Janis; Standley, Eric A.; Tasker, Sarah Z. Bis(1,5-cyclooctadiene)nickel(0). Encyclopedia of Reagents for Organic Synthesis (American Cancer Society). 2015: 1–15. doi:10.1002/047084289x.rb118.pub3 (英语). 
  6. ^ Olivier-Bourbigou, H.; Breuil, P. A. R.; Magna, L.; Michel, T.; Espada Pastor, M. Fernandez; Delcroix, D. Nickel Catalyzed Olefin Oligomerization and Dimerization. Chemical Reviews. 2020, 120 (15): 7919–7983. PMID 32786672. doi:10.1021/acs.chemrev.0c00076. 
  7. ^ Martin F. Semmelhack and Paul M. Helquist (1988). "Reaction of Aryl Halides with π-Allylnickel Halides: Methallylbenzene". Org. Synth. 52: 115; Coll. Vol. 6: 161. 
  8. ^ Danopoulos, Andreas A.; Simler, Thomas; Braunstein, Pierre. N-Heterocyclic Carbene Complexes of Copper, Nickel, and Cobalt. Chemical Reviews. 2019, 119 (6): 3730–3961. PMID 30843688. doi:10.1021/acs.chemrev.8b00505. 
  9. ^ Göttker-Schnetmann, Inigo; Mecking, Stefan. A Practical Synthesis of [(tmeda)Ni(CH3)2], Isotopically Labeled [(tmeda)Ni(13CH3)2], and Neutral Chelated-Nickel Methyl Complexes. Organometallics. 2020, 39 (18): 3433–3440. doi:10.1021/acs.organomet.0c00500. 
  10. ^ Reppe, Walter; Schlichting, Otto; Klager, Karl; Toepel, Tim. Cyclisierende Polymerisation von Acetylen. I. Über Cyclooctatetraen [Ring-forming polymerization of acetylene. I. Cyclooctatetraene]. Justus Liebigs Annalen der Chemie. 1948, 560 (1): 1–92. doi:10.1002/jlac.19485600102. 
  11. ^ Jen-Chieh Hsieh and Chien-Hong Cheng. Nickel-catalyzed cocyclotrimerization of arynes with diynes; a novel method for synthesis of naphthalene derivatives. Chemical Communications. 2005, 2005 (19): 2459–2461. PMID 15886770. doi:10.1039/b415691a. 
  12. ^ Formation of an Aza-nickelacycle by Reaction of an Imine and an Alkyne with Nickel(0): Oxidative Cyclization, Insertion, and Reductive Elimination Sensuke Ogoshi Haruo Ikeda, and Hideo Kurosawa Angew. Chem. Int. Ed. 2007, 46, 4930 –4932 doi: 10.1002/anie.200700688
  13. ^ Reaction of the imine N-(benzenesulfonyl)benzaldimine with two equivalents of diphenylacetylene with NiCOD2 and tricyclohexylphosphine first to nickelapyrroline and with a second insertion a nickeldihydroazepine and finally on heating a dihydropyridine
  14. ^ Kohei Tamao, Koji Sumitani, Makoto Kumada. Selective carbon-carbon bond formation by cross-coupling of Grignard reagents with organic halides. Catalysis by nickel-phosphine complexes. J. Am. Chem. Soc. 1972, 94 (12): 4374–4376. doi:10.1021/ja00767a075. 
  15. ^ Anthony O. King, Nobuhisa Okukado and Ei-ichi Negishi. Highly general stereo-, regio-, and chemo-selective synthesis of terminal and internal conjugated enynes by the Pd-catalysed reaction of alkynylzinc reagents with alkenyl halides. Journal of the Chemical Society Chemical Communications. 1977: 683. doi:10.1039/C39770000683. 
  16. ^ Strategic Applications of Named Reactions in Organic Synthesis Laszlo Kurti, Barbara Czako Academic Press (March 4, 2005) ISBN 0-12-429785-4