Organonickel

Organonickel chemistry is a branch of organometallic chemistry that deals with organic compounds featuring nickel-carbon bonds.[1][2] They are used as a catalyst, as a building block in organic chemistry and in chemical vapor deposition. Organonickel compounds are also short-lived intermediates in organic reactions. The first organonickel compound was nickel tetracarbonyl Ni(CO)₄, reported in 1890 and quickly applied in the Mond process for nickel purification. Organonickel complexes are prominent in numerous industrial processes including carbonylations, hydrocyanation, and the Shell higher olefin process.

organonickel

Overview

Bis(1,5-cyclooctadiene)nickel(0)

Many complexes exist of nickel coordinated to an alkene. In these compounds nickel is formally zerovalent Ni⁰ and the bonding is described with the Dewar–Chatt–Duncanson model. One common representative is Bis(cyclooctadiene)nickel(0) (Ni(COD)₂), which contains two cyclooctadiene ligands. It is a 18VE compound with 10 electrons provided by nickel itself and 4x2 electrons more by the double bonds. This solid, which melts at 60 °C,[3] is used as a catalyst and as a precursor for many other nickel compounds.

Ni allyl complexes

Allylnickel(II) bromide dimer.

Allyl halides react with Ni(CO)₄ to form pi-allyl complexes, (allyl)₂Ni₂Cl₂.[4] These compounds in turn are sources of allyl nucleophiles. In (allyl)₂Ni₂Br₂ and (allyl)Ni(C₅H₅), nickel is assigned to oxidation number +2, and the electron counts are 16 and 18, respectively.

Cyclopentadienyl complexes

Nickelocene

Nickelocene NiCp₂ with +2 Ni oxidation state and 20 valence electrons is the main metallocene of nickel. It can be oxidized by one electron. The corresponding palladocene and platinocene are unknown. From nickelocene, many derivatives are generated, e.g. CpNiLCl, CpNiNO, and Cp₂Ni₂(CO)₃.

Nickel carbene complexes

Nickel forms carbene complexes, formally featuring C=Ni double bonds.

Alkyl and aryl precatalysts

A variety of Ni(II) alkyl and aryl complexes are known. Examples include [(dppf)Ni(cinnamyl)Cl)], trans-(PCy₂Ph)₂Ni(o-tolyl)Cl]], (dppf)Ni(o-tolyl)Cl]], (TMEDA)Ni(o-tolyl)Cl, and (TMEDA)NiMe₂.

Synthesis of [(TMEDA)Ni(o-tolyl)Cl].[5]

Nickel compounds of the type NiR₂ also exist with just 12 valence electrons. In solution however solvent always interact with the metal atom increasing the electron count. One 12 VE compound is di(mesityl)nickel prepared from (allyl)₂Ni₂Br₂ and the corresponding Grignard reagent.

(allyl)₂Ni₂Br₂ + 4 C₆H₂Me₃MgBr → 2 (allyl)MgBr + 2 MgBr₂ + 2 (C₆H₂Me₃)₂Ni

Reactions

Alkene/alkyne oligomerizations

Nickel compounds catalyze the oligomerization of alkenes and alkynes. This property validated the research and development of Ziegler–Natta catalysts in the 1950s. That discovery shown by nickel impurities originating from an autoclave which killed the propagation reaction (Aufbau) in favor of termination reaction to a terminal alkene: the polymerization of ethylene suddenly stopped at 1-butene. This so-called nickel effect prompted the search for other catalysts capable of this reaction, with results in the finding of new catalysts that technically produced high molar mass polymers, like the modern Ziegler–Natta catalysts.

One practical implementation of alkyne oligomerization is the Reppe synthesis; for example in the synthesis of cyclooctatetraene:

This is a formal [2+2+2+2]cycloaddition. The oligomerization of butadiene with ethylene to trans-1,4-hexadiene was an industrial process at one time.

Formal [2+2+2]cycloadditions also take place in alkyne trimerisation. This extensible trimerisation can generally include benzyne.[6] Benzyne is generated in situ from a benzene compound attached to a triflate and a trimethylsilyl substituent in the ortho- positions and reacts with a di-yne such as 1,7-octadiyne along with a nickel(II) bromide / zinc catalyst system (NiBr₂ bis(diphenylphosphino) ethane / Zn) to synthesize the corresponding naphthalene derivative.

In the catalytic cycle elementary zinc serves to reduce nickel(II) to nickel(0) to which can then coordinate two alkyne bonds. A cyclometalation step follows to the nickelcyclopentadiene intermediate and then coordination of the benzyne which gives a C-H insertion reaction to the nickelcycloheptatriene compound. Reductive elimination liberates the tetrahydroanthracene compound.

The formation of organonickel compounds in this type of reaction is not always obvious but in a carefully designed experiment two such intermediates are formed quantitatively:[7][8]

It is noted in one study [9] that this reaction only works with acetylene itself or with simple alkynes due to poor regioselectivity. From a terminal alkyne 7 isomers are possibly differing in the position of the substituents or the double bond positions. One strategy to remedy this problem employs certain diynes:

The selected reaction conditions also minimize the amount formed of competing [2+2+2]cycloaddition product to the corresponding substituted arene.

Coupling reactions

Nickel compounds cause the coupling reaction between allyl and aryl halides. Other coupling reactions involving nickel in catalytic amounts are the Kumada coupling and the Negishi coupling.

Ni carbonylation

Ni catalyzes the addition of carbon monoxide to alkenes and alkynes. The industrial production of acrylic acid at one time consisted of combining acetylene, carbon monoxide and water at 40-55 atm and 160-200 °C with nickel(II) bromide and a copper halide.

See also

• Nickel(II) precatalysts

References

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. 244988 Bis 1 5 cyclooctadiene nickel 0
4. Martin F. Semmelhack and Paul M. Helquist (1988). "Reaction of Aryl Halides with π-Allylnickel Halides: Methallylbenzene". Organic Syntheses. 52: 115.; Collective Volume, 6, p. 161
5. Shields, Jason D.; Gray, Erin E.; Doyle, Abigail G. (2015-05-01). "A Modular, Air-Stable Nickel Precatalyst". Organic Letters. 17 (9): 2166–2169. doi:10.1021/acs.orglett.5b00766. PMC 4719147. PMID 25886092.
6. Jen-Chieh Hsieh and Chien-Hong Cheng (2005). "Nickel-catalyzed cocyclotrimerization of arynes with diynes; a novel method for synthesis of naphthalene derivatives". Chemical Communications. 2005 (19): 2459–2461. doi:10.1039/b415691a. PMID 15886770.
7. 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
8. 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
9. Nickel(0)-Catalyzed [2 + 2 + 2 + 2] Cycloadditions of Terminal Diynes for the Synthesis of Substituted Cyclooctatetraenes Paul A. Wender and Justin P. Christy J. Am. Chem. Soc.; 2007; 129(44) pp 13402 - 13403; (Communication) doi:10.1021/ja0763044