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Issue 25, 2013
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A well-defined model system for the chromium-catalyzed selective oligomerization of ethylene

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Abstract

The chromium(I) dinitrogen complex [(i-Pr2Ph)2nacnacCr]2(μ–η22-N2) catalyzes the selective trimerization of ethylene to 1-hexene at ambient pressure and temperature, and in the absence of any cocatalyst. After the conversion of the substrate, the catalyst cleanly converts to another chromium(I) species, namely [(i-Pr2Ph)2nacnacCr]2(μ–η22-C2H4), which is not catalytically active. Binuclear metallacycles containing Cr(II) have been prepared as candidates for catalytically active intermediates; however they are not kinetically competent to explain the catalysis. Turning thus to mononuclear metallacycles featuring Cr(III), a chromacyclopentane, chromacyclopentene and chromacyclopentadiene have been prepared as models of catalytic intermediates. Of these, the latter also catalyzes the trimerization of ethylene. These results support the proposal that selective ethylene oligomerization catalysis involves an interplay between Cr(I) ethylene complexes and mononuclear Cr(III) metallacycles.

Graphical abstract: A well-defined model system for the chromium-catalyzed selective oligomerization of ethylene

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Publication details

The article was received on 11 Jan 2013, accepted on 06 Mar 2013 and first published on 06 Mar 2013


Article type: Paper
DOI: 10.1039/C3DT00109A
Citation: Dalton Trans., 2013,42, 9198-9210
  • Open access: Creative Commons BY license
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    A well-defined model system for the chromium-catalyzed selective oligomerization of ethylene

    W. H. Monillas, J. F. Young, G. P. A. Yap and K. H. Theopold, Dalton Trans., 2013, 42, 9198
    DOI: 10.1039/C3DT00109A

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