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Synthesis, Characterization and Ethylene Oligomerization Studies of Nickel Complexes Bearing Novel Bis-α-diimine Ligands

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Abstract

Sterically modulated, diazine bridged bis-α-diimine Ni(II) complexes have been synthesized to provide a versatile set of catalytic systems for ethylene oligomerization in combination with methyl aluminoxane (MAO) as cocatalyst. All the dinickel catalysts efficiently oligomerize ethylene to produce C4–C20 fractions at activities of up to 1,123 kg-oligomer mol-Ni−1 bar−1 h−1 at 30 °C with Al(MAO)/Ni ratio at 300. The change in potential of metal center induced by substituents, as evidenced by cyclic voltammetric measurements, influences the oligomerization activity. Complexes C1 and C3 produces traces of polyethylene at 30 °C, while at higher temperature all the complexes yielded oligomers only.

Graphical Abstract

A series of sterically modulated binuclear nickel(II) complexes of three novel bis-α-diimine ligands have been synthesized. The square planar dinickel(II) center complexes efficiently oligomerize ethylene to C4–C20 fractions showing high selectivity towards 1-butene as nearly as 75 % of the total C4 content

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Acknowledgments

The authors thank USIC, Karnatak University, Dharwad, for providing spectral facilities. Recording of NMR and IR spectra from IIT-Madras and IIT-Bombay is gratefully acknowledged. One of the authors (Sandeep P. Netalkar) is thankful to Department of Science & Technology for providing financial assistance under INSPIRE fellowship program.

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Correspondence to Vidyanand K. Revankar.

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Dedicated to our teacher, Professor S.T. Nandibewoor on the occasion of his 60th birthday.

Electronic Supplementary Material

CCDC 938649 and CCDC 913669 contain the supplementary crystallographic data for ligand L1 and L3 respectively. This data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk. For crystallographic data in table format, ESI–MS spectra and TG–DTA thermogram of C1 see Supplementary material.

Supplementary material 1 (DOCX 338 kb)

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Netalkar, S.P., Netalkar, P.P., Sathisha, M.P. et al. Synthesis, Characterization and Ethylene Oligomerization Studies of Nickel Complexes Bearing Novel Bis-α-diimine Ligands. Catal Lett 144, 181–191 (2014). https://doi.org/10.1007/s10562-013-1123-2

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