Highly active ethylene oligomerization catalysts
Organometallics. Bd. 30. H. 12. Washington, DC: ACS Publ. 2011 S. 3346 - 3352
Erscheinungsjahr: 2011
ISBN/ISSN: 1520-6041
Publikationstyp: Zeitschriftenaufsatz
Sprache: Englisch
Doi/URN: 10.1021/om2002359
Inhaltszusammenfassung
Reaction of RN(H)PBr(Ph)2N(H)R [R = t-Bu, i-Pr, Ph] with two equiv. of BuLi followed by reaction with CrCl2(THF)2 afforded the divalent Cr complexes [(t-Bu)NP(Ph)2N(t-Bu)]Cr(?2-Cl)2Li(THF)2 (1), [(i-Pr)NP(Ph)2N(i-Pr)]Cr(?2-Cl)2Li(THF)2 (2), and [{[(Ph)NP(Ph)2N(Ph)]Cr}2(?2-Cl)3][Li(DME)3] (3). The trivalent analog of 1, {[(t-Bu)NP(Ph)2N(t-Bu)]Cr(?2-Cl)3(?3-Cl)2}{Li (THF)2} (4), was obtained in a similar manner via treatment of the double deprotonated ligand with CrCl3(THF)3. Both reactions o...Reaction of RN(H)PBr(Ph)2N(H)R [R = t-Bu, i-Pr, Ph] with two equiv. of BuLi followed by reaction with CrCl2(THF)2 afforded the divalent Cr complexes [(t-Bu)NP(Ph)2N(t-Bu)]Cr(?2-Cl)2Li(THF)2 (1), [(i-Pr)NP(Ph)2N(i-Pr)]Cr(?2-Cl)2Li(THF)2 (2), and [{[(Ph)NP(Ph)2N(Ph)]Cr}2(?2-Cl)3][Li(DME)3] (3). The trivalent analog of 1, {[(t-Bu)NP(Ph)2N(t-Bu)]Cr(?2-Cl)3(?3-Cl)2}{Li (THF)2} (4), was obtained in a similar manner via treatment of the double deprotonated ligand with CrCl3(THF)3. Both reactions of the divalent 1 or trivalent 4 with AlMe3 yielded the trivalent and cationic complex {[(t-Bu)NP(Ph)2N(t-Bu)]2Cr}{(Me3Al)2Cl}·toluene (5). Upon activation with MAO, 1-3 produced unprecedented and potentially useful catalytic systems for nonselective ethylene oligomerization devoid of polymer. Divalent Cr is clearly the species responsible for the catalytic behavior, ruling out that nonselective oligomerization proceeds via a redox metallacycle mechanism. The absence of polymer in combination with the record activity makes 1 competitive with the best performing industrially used systems.» weiterlesen» einklappen
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Klassifikation
DFG Fachgebiet:
Molekülchemie
DDC Sachgruppe:
Zeitschriften, fortlaufende Sammelwerke