有機鎳化學

有機鎳化學是一門研究含有碳-鎳化學鍵的化合物（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的催化劑。

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的雙(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，例如可以用於殼牌高級烯烴過程（英語：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)₂Ni₂Cl₂^[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]

—

${\ce {Ni(CH3)2(TMEDA)}}$ 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]。

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]。鋅可以把二價鎳還原成零價鎳。

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、順反異構化和還原消去幾部分：

鎳化合物亦可用於根岸偶聯反應，其中有機鋅試劑與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和鹵化銅作爲催化劑：

Nickel catalyzed carbonylation of acetylene to acrylic acid

參見

參考資料

^ F.A. Carey R.J. Sundberg Advanced Organic Chemistry 2nd Ed. ISBN 0-306-41199-7
^ Comprehensive organometallic chemistry III Robert Crabtree, Mike Mingos 2006 ISBN 0-08-044590-X
^ Wilke, G. Contributions to Organo-Nickel Chemistry. Angewandte Chemie International Edition. 1988, 27 (1): 185–206. doi:10.1002/anie.198801851.
^ 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 (幫助)
^ 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 （英語）.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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
^ 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
^ 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.
^ 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.
^ Strategic Applications of Named Reactions in Organic Synthesis Laszlo Kurti, Barbara Czako Academic Press (March 4, 2005) ISBN 0-12-429785-4

[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 (幫助)

[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 （英語）.

[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.

[reppe-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

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