Triazacyclohexane Chromium Triflate Complexes as Precursors for the Catalytic Selective Olefin Trimerisation and its Investigation by Mass Spectrometry

Randolf Köhn, Alex Coxon, Samaphon Chunawat, Callum Heron, Shahram Mihan, Catherine Lyall, Shaun Reeksting, Gabriele Kociok-Kohn

Research output: Contribution to journalArticle

Abstract

A novel set of linear α-olefin trimerisation pre-catalysts is presented. The R3TACCr(OTf)3 (R3TAC = 1,3,5-trialkyl-1,3,5-triazacyclohexane) complexes produce an active system after facile activation with less than 10 equivalents of trialkylaluminium. Isomerisation was observed in many cases, which is proposed to occur via the π-allyl complex mechanism, though this was minimised by optimisation of the reaction conditions. The pre-catalysts can be synthesised from R3TACCrCl3 in neat TfOH or by addition of R3TAC to Cr(OTf)3 or better Cr(OTf)3(THF)3, the synthesis and structure of which is presented here. The use of this highly defined system allowed the identification of 2-methyl-1-hexene as a side product of activation with AlMe3, in agreement with the proposed metallacyclic mechanism. Isomer distribution of the trimer product is similar to R3TACCrCl3/MAO activated systems and depends mostly on the ligand substituent R. ESI mass spectrometry of an ortho-difluorobenzene solution of the activated catalyst was analysed at different stages of reaction. A series of signals was observed that matched those expected for cationic chromium species predicted by the metallacyclic mechanism. In particular, [R3TACCrMe2]+ was observed to form immediately after alkylation with AlMe3, while [R3TACCr(olefin)n]+ (n = 0, 1, 2, 3, 4 and olefin = 1-hexene or 1-octene) formed after addition of 1-hexene. Absence of any detected tetramer and observation of [R3TACCr(olefin)4]+ leads to the conclusion that a metallacycloheptane-olefin complex may lead to β-H abstraction rather than insertion and may even be required to avoid formation of [R3TACCr(olefin)1]+ which is observed in only very small amounts indicating a low stability. Chromium(I) complexes [R3TACCr(arene)]+ with the arene solvent can also be observed and their signal intensity indicate a relative stability of o-C6H4F2 < cymene < benzene < PhF, toluene < p-xylene.
Original languageEnglish
Article number114572
JournalPolyhedron
Volume185
Early online date23 Apr 2020
DOIs
Publication statusPublished - 15 Jul 2020

Keywords

  • Catalysis
  • Chromium
  • Coordination chemistry
  • Electrospray mass spectrometry
  • Selective olefin trimerisation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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