Direct Base-Assisted C‒H Cyclonickelation of 6-Phenyl-2,2′-bipyridine

The organonickel complexes [Ni(Phbpy)X] (X = Br, OAc, CN) were obtained for the first time in a direct base-assisted arene C(sp2)–H cyclometalation reaction from the rather unreactive precursor materials NiX2 and HPhbpy (6-phenyl-2,2′-bipyridine) or from the versatile precursor [Ni(HPhbpy)Br2]2. Dif...

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Bibliographic Details
Published in:Molecules (Basel, Switzerland) Vol. 25; no. 4; p. 997
Main Authors: Vogt, Nicolas, Sivchik, Vasily, Sandleben, Aaron, Hörner, Gerald, Klein, Axel
Format: Journal Article
Language:English
Published: Switzerland MDPI AG 24.02.2020
MDPI
Subjects:
base-assisted
Catalysis
Cations, Divalent
Chemistry Techniques, Synthetic
Coordination Complexes - chemical synthesis
Cycloaddition Reaction
cyclometalation
cyclonickelation
c–h activation
Decomposition
Experiments
Humans
Ligands
Models, Chemical
Nickel
Nickel - chemistry
organonickel
Oxidation-Reduction
Pyridines - chemistry
Stereoisomerism
organonickel
cyclometalation
C–H activation
base-assisted
cyclonickelation
ISSN:1420-3049, 1420-3049
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Summary:The organonickel complexes [Ni(Phbpy)X] (X = Br, OAc, CN) were obtained for the first time in a direct base-assisted arene C(sp2)–H cyclometalation reaction from the rather unreactive precursor materials NiX2 and HPhbpy (6-phenyl-2,2′-bipyridine) or from the versatile precursor [Ni(HPhbpy)Br2]2. Different from previously necessary C‒Br oxidative addition at Ni(0), an extended scan of reaction conditions allowed quantitative access to the title compound from Ni(II) on synthetically useful timescales through base-assisted C‒H activation in nonpolar media at elevated temperature. Optimisation of the reaction conditions (various bases, solvents, methods) identified 1:2 mixtures of acetate and carbonate as unrivalled synergetic base pairs in the optimum protocol that holds promise as a readily usable and easily tuneable access to a wide range of direct nickelation products. While for the base-assisted C‒H metalation of the noble metals Ru, Ir, Rh, or Pd, this acetate/carbonate method has been established for a few years, our study represents the leap into the world of the base metals of the 3d series.
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ISSN:1420-3049
1420-3049
DOI:10.3390/molecules25040997