有机镍化学

有机镍化学是一门研究含有碳-镍化学键的化合物（有机镍化合物）的理化性质、合成与反应的学科，是有机金属化学的分支^[1]^[2] 。四羰基镍是第一个被人类合成的有机镍化合物，被化学家路德维希·蒙德在1890年首度合成。它立刻被用于蒙德法来提炼镍金属。随后有机镍化合物用于不同过渡金属催化反应的催化剂。

分类与合成

在镍化合物中，镍的氧化数多为0或者+2。有很多镍的烷基或芳基配合物的化学式都是NiR(X)L₂。而NiR₂类的镍配合物有时只有12个价电子，而他们会透过溶剂化来增加自己的价电子数，稳定自己。

而镍的烯烃配合物较为常见。例如具备两个环辛二烯配体的双(1,5-环辛二烯)镍，它是一个18电子的配合物，其中有去10个电子由镍提供，而剩余的4×2个电子有配体的双键提供。它对空气极为敏感^[3]，可溶于有机溶剂^[4]^[5]。镍的烯烃配合物有较多实际的用途，例如可以用于壳牌高级烯烃过程（英语：Shell Higher Olefin Process）^[6]等烯烃的聚合反应中。

烯丙基型卤代烃可以与四羰基镍反应生成(烯丙基)₂Ni₂Cl₂^[7]。它是一种π-烯丙基配合物，镍的氧化数为+2，是烯丙基亲核试剂的来源。

镍亦可以跟卡宾生成配合物，其中包含碳-镍双键： ^[8]

—

${\ce {Ni(CH3)2(TMEDA)}}$ 是一个常用的试剂^[9]。

反应

烯烃或炔烃的低聚

镍化合物可以催化烯烃或炔烃的低聚。例如在氰化镍的存在下，乙炔四聚成环辛四烯^[10]。

溴化镍、锌可以成为 [2+2+2]环加成反应的催化剂，反应涉及到苯炔^[11]。锌可以把二价镍还原成零价镍。

在这些实验中，镍配合物的存在可能不太明显，但如果细心地设计实验，镍配合物中间体便可以定量生成^[12]^[13]：

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

偶联反应

镍配合物可以催化烯丙基或芳基卤代烃的偶联反应：

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

而催化量的镍化合物亦可用于熊田偶联反应^[14]，机理跟其他很多金属催化的反应一样，经历氧化加成、转金属化、顺反异构化和还原消去几部分：

镍化合物亦可用于根岸偶联反应，其中有机锌试剂与卤代烃在镍配合物的催化下发生偶联，生成一个新的C－C键^[15]^[16]：

羰基化

镍催化烯烃和炔烃的羰基化反应。丙烯酸的工业合成曾经用到溴化镍和卤化铜作为催化剂：

Nickel catalyzed carbonylation of acetylene to acrylic acid

参见

参考资料

^ 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 (帮助)
^ 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 （英语）.
^ 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 (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.

[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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[2]

[3]

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[5]

[6]

[7]

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