Methylaluminoxane-Free Chromium Catalytic System for Ethylene Tetramerization.

Ethylene tetramerization catalyst systems comprising a Cr(III) complex containing PNP ligands and methylaluminoxane (MAO) are useful for the production of 1-octene. However, a concern with these systems is the use of expensive MAO in excess. Herein, we report a catalytic system that avoids the use of MAO. Metathesis of CrCl3(THF)3 and [(CH3CN)4Ag]+[B(C6F5)4]- afforded [L4CrIIICl2]+[B(C6F5)4]- (L = CH3CN or tetrahydrofuran (THF)), which was converted to [(PNP)CrCl2L2]+[B(C6F5)4]-, where PNP is iPrN(PPh2)2 (1) or [CH3(CH2)16]2CHN(PPh2)2 (2). The molecular structures of [(THF)4CrIIICl2]+[B(C6F5)4]- and [1-CrCl2(THF)2]+[B(C6F5)4]- were unambiguously determined by X-ray crystallography. The cationic (PNP)CrIII complexes paired with [B(C6F5)4]- anions, that is, [(PNP)CrCl2(CH3CN)2]+[B(C6F5)4]-, exhibited high activity in chlorobenzene when activated with common trialkylaluminum species (Me3Al, Et3Al, and iBu3Al). The activities and selectivity were comparable to those of the original MAO-based Sasol system (1-CrCl3/MAO). When activated with Et3Al or iBu3Al, the Cr complex, [2-CrCl2(CH3CN)2]+[B(C6F5)4]-, which bears long alkyl chains, showed high activity in the more desirable methylcyclohexane solvent (89 kg/g-Cr/h) and much higher activity in cyclohexene (168 kg/g-Cr/h). Other advantages of the [2-CrCl2(CH3CN)2]+[B(C6F5)4]-/Et3Al system in cyclohexene were negligible catalyst deactivation, formation of only a negligible amount of polyethylene side product (0.3%), and formation of fewer unwanted side products above C10. The [B(C6F5)4]- anion is compatible with trialkylaluminum species once it is not paired with a trityl cation. Hence, [(PNP)CrCl2(CH3CN)2]+[B(C6F5)4]-/Et3Al exhibited a significantly higher activity than that of a previously reported system composed of [Ph3C]+[B(C6F5)4]-, that is, 1/CrCl3(THF)3/[Ph3C]+[B(C6F5)4]-/Et3Al.

Correction to "Methylaluminoxane-Free Chromium Catalytic System for Ethylene Tetramerization".

[This corrects the article DOI: 10.1021/acsomega.6b00506.].

A chromium precursor for the Phillips ethylene trimerization catalyst: (2-ethylhexanoate)2CrOH.

The conventional Phillips ethylene trimerization catalyst prepared by reacting Cr(EH)3 (EH = 2-ethylhexanoate), 2,5-dimethylpyrrole (Me2C4H2NH), Et3Al, and Et2AlCl in an aromatic hydrocarbon solvent was improved to obtain a congener composed of a new chromium precursor (EH)2CrOH, (Me2C4H2N)AlEt2, and Et3Al·ClAlEt2. Reaction of CrCl3 with 3 equiv. Na(EH) in water did not generate Cr(EH)3, but unexpectedly produced (EH)2CrOH. In comparison with the erratic catalytic performance of the original Phillips system, due to the ill-defined nature of the Cr(EH)3 source (16 or 6.8 × 10(6) g per mol-Cr h depending on the source), the improved system exhibited consistently high activity (54 × 10(6) g per mol-Cr h). Reaction of (EH)2CrOH with (Me2C4H2N)AlMe2·OEt2 afforded the dimeric Cr(II)-complex (6) coordinated by (η(5)-Me2C4H2N)AlMe2(NC4H2Me2) and µ2-κ(1):η(2)-Me2C4H2N ligands. 6 provided highly active species when activated with Et3Al·ClAlEt2.