Many alkyl and aryl complexes are known with the formula NiR(X)L2. 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, (TMEDA)Ni(Br)(C6F5).[1]
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.
Many complexes exist of nickel coordinated to an alkene. Practical applications of this theme include polymerization or oligomerization of alkenes, as in the Shell Higher Olefin Process.[7] 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, is used as a catalyst and as a precursor for many other nickel compounds.
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.
Carbene complexes
Nickel forms carbene complexes, formally featuring C=Ni double bonds.[9]
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:
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:[11][12]
It is noted in one study [13] 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:
↑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 Script error: No such module "CS1 identifiers".
↑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
↑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) Script error: No such module "CS1 identifiers".
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