查看“︁有机镍化学”︁的源代码

'''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<ref>F.A. Carey R.J. Sundberg ''Advanced Organic Chemistry'' 2nd Ed. {{ISBN|0-306-41199-7}}</ref><ref>''Comprehensive organometallic chemistry'' III Robert Crabtree, Mike Mingos 2006  {{ISBN|0-08-044590-X}}</ref> 。[[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]]。
[[File:Organonickel.png|right|150px|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)L<sub>2</sub>。而NiR<sub>2</sub>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<ref>{{cite journal | authorlink = Günther Wilke | author = Wilke, G. | title = Contributions to Organo-Nickel Chemistry | journal = Angewandte Chemie International Edition | year = 1988 | volume = 27 | issue = 1 | pages = 185–206 | doi = 10.1002/anie.198801851 }}</ref>，可溶於有機溶劑<ref>{{Cite book| author1 = Schunn, R. A. | authorlink2 = Steven Ittel | author2 = Ittel, S. D. | author3 = Cushing, M. A. | title = Bis(1,5-Cyclooctadiene)Nickel(0) | journal = [[Inorganic Syntheses]] | year = 1990 | volume = 28 | pages = 94–98 | doi = 10.1002/9780470132593.ch25 | isbn = 978-0-470-13259-3}}</ref><ref>{{cite journal |last1=Wender |first1=Paul A. |last2=Smith |first2=Thomas E. |last3=Duong |first3=Hung A. |last4=Louie |first4=Janis |last5=Standley |first5=Eric A. |last6=Tasker |first6=Sarah Z. |title=Bis(1,5-cyclooctadiene)nickel(0) |journal=Encyclopedia of Reagents for Organic Synthesis |date=2015 |pages=1–15 |doi=10.1002/047084289x.rb118.pub3 |url=  |publisher=American Cancer Society |language=en}}</ref>。鎳的烯烴配合物有較多實際的用途，例如可以用於{{link-en|壳牌高级烯烃过程|Shell Higher Olefin Process}}<ref>{{cite journal |doi=10.1021/acs.chemrev.0c00076|title=Nickel Catalyzed Olefin Oligomerization and Dimerization|year=2020|last1=Olivier-Bourbigou|first1=H.|last2=Breuil|first2=P. A. R.|last3=Magna|first3=L.|last4=Michel|first4=T.|last5=Espada Pastor|first5=M. Fernandez|last6=Delcroix|first6=D.|journal=Chemical Reviews|volume=120|issue=15|pages=7919–7983|pmid=32786672}}</ref>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)<sub>2</sub>Ni<sub>2</sub>Cl<sub> 2</sub><ref>{{OrgSynth|author=Martin F. Semmelhack and Paul M. Helquist|year=1988|title=Reaction of Aryl Halides with π-Allylnickel Halides: Methallylbenzene|volume=52|pages=115|collvol=6|collvolpages=161|prep=CV6P0722}}</ref>。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：
<ref>{{cite journal |doi=10.1021/acs.chemrev.8b00505|title=N-Heterocyclic Carbene Complexes of Copper, Nickel, and Cobalt|year=2019|last1=Danopoulos|first1=Andreas A.|last2=Simler|first2=Thomas|last3=Braunstein|first3=Pierre|journal=Chemical Reviews|volume=119|issue=6|pages=3730–3961|pmid=30843688}}</ref>
:[[File:NiCarbenes.png|400px|Nickel carbenes]]{{--}}

<chem>Ni(CH3)2(TMEDA)</chem>是一個常用的試劑<ref>{{cite journal |doi=10.1021/acs.organomet.0c00500|title=A Practical Synthesis of &#91;(tmeda)Ni(CH<sub>3</sub>)<sub>2</sub>&#93;, Isotopically Labeled &#91;(tmeda)Ni(<sup>13</sup>CH<sub>3</sub>)<sub>2</sub>&#93;, and Neutral Chelated-Nickel Methyl Complexes|year=2020|last1=Göttker-Schnetmann|first1=Inigo|last2=Mecking|first2=Stefan|journal=Organometallics|volume=39|issue=18|pages=3433–3440}}</ref>。
==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]]<ref name=reppe>{{cite journal
 | title = Cyclisierende Polymerisation von Acetylen. I. Über Cyclooctatetraen|trans-title=Ring-forming polymerization of acetylene. I. Cyclooctatetraene
 | author-link = Walter Reppe|first1=Walter|last1=Reppe|first2=Otto|last2=Schlichting|first3=Karl|last3=Klager|first4=Tim|last4=Toepel
 | journal = [[Justus Liebigs Annalen der Chemie]]
 | volume = 560
 | issue = 1
 | pages = 1–92
 | year = 1948
 | doi = 10.1002/jlac.19485600102}}
</ref>。
:[[File:Reppe Synthesis COT.svg|frameless|upright=1.5|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]]<ref>{{cite journal | title = Nickel-catalyzed cocyclotrimerization of arynes with diynes; a novel method for synthesis of naphthalene derivatives | author = Jen-Chieh Hsieh and Chien-Hong Cheng | journal = [[Chemical Communications]] | year = 2005 | volume = 2005 | issue = 19 | pages = 2459–2461 | doi = 10.1039/b415691a| pmid = 15886770 }}</ref>。[[鋅]]可以把二價鎳還原成零價鎳。
[[File:AlkyneTrimerizationInvolvingAnAryne.png|400px|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<ref>''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}}</ref><ref>Reaction of the [[imine]] N-(benzenesulfonyl)benzaldimine with two equivalents of [[diphenylacetylene]] with NiCOD<sub>2</sub> and [[tricyclohexylphosphine]] first to nickelapyrroline and with a second insertion a nickeldihydroazepine and finally on heating a [[dihydropyridine]]</ref>：
:[[File:Nickeldihydroazepine.png|400px|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]]：
:[[File:Organonickelcouplings.png|400px|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]]<ref>{{cite journal en| title = Selective carbon-carbon bond formation by cross-coupling of Grignard reagents with organic halides. Catalysis by nickel-phosphine complexes | author = Kohei Tamao, Koji Sumitani, Makoto Kumada | journal = [[J. Am. Chem. Soc.]] | year = 1972 | volume = 94 | issue = 12 | pages = 4374–4376 | doi = 10.1021/ja00767a075}}</ref>，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：
[[File:Katalysezyklus-Kumada-Kupplung.png|center|500px|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]]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<ref>{{cite journal en| author = Anthony O. King, Nobuhisa Okukado and [[Ei-ichi Negishi]] | doi = 10.1039/C39770000683 | title = 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 | year = 1977 | journal = Journal of the Chemical Society Chemical Communications | pages = 683}}</ref><ref>''Strategic Applications of Named Reactions in Organic Synthesis'' Laszlo Kurti, Barbara Czako Academic Press (March 4, '''2005''') ISBN 0-12-429785-4</ref>：
[[File:NickelMechanism.png|center|frameless|373x373px]]{{-}}
===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：
:[[File:NickelCatalyzedCarbonylation.png|400px|Nickel catalyzed carbonylation of acetylene to acrylic acid]]
==參見==
{{ChemicalBondsToCarbon}}
==參考資料==
{{reflist}}
[[Category:有机鎳化合物| ]]