Synthesis and Catalytic Oligomerization Activity of Chromium Catalysts of Ligand Systems with Switchable Connectivity

Abstract

Nucleophilic attack of in situ generated bis(diphenylphosphino)methane (DPPM – ) anion at CO 2, CyNCO, t -BuNCO, 2,6-( i -Pr) 2 PhNCO, and 2,4,6-(Me 3 )PhNCO resulted in the formation of the novel anionic ligands {[(Ph 2 P) 2 CHCO 2 ]Li(THF) 2 } 2 ( 1 ), {[(Ph 2 P) 2 C═CNH(R)O]Li(OEt) 2 } 2 (R = Cy ( 2 ), R = t -Bu ( 3 )), [Ph 2 PCH═P(Ph 2 )C═N(2,6- i- Pr 2 C 6 H 3 )O]Li(OEt 2 ) 2 ( 4 ), and {[(Ph 2 P) 2 C═CNH(2,4,6-Me 3 C 6 H 2 )O]Li] n ( 5 ), respectively. Ligand 4, however, showed a connectivity resulting from a nonclassical type of attack where the P atom acted as a nucleophilc center, thus affording a mixed-valent P(III)/P(V) species. Instead, the closely similar 5 showed a classical type of connectivity. The reaction of the in situ generated DPPM – anion with 1 and 0.5 equiv of CrCl 3 (THF) 3 gave the chelated chromium complexes [HC(PPh 2 ) 2 ]Cr[(μ-Cl) 2 Li(THF) 2 ] 2 ( 6 ) and [HC(PPh 2 ) 2 ] 2 Cr(μ-Cl) 2 Li(THF) 2 ]·1.5THF ( 7 ), respectively. The reaction of ligand 1 with CrCl 2 (THF) 2 afforded the dimeric [{[(Ph 2 P) 2 C(H)CO 2 ] 2 }Cr(THF)] 2 ( 8 ), whereas the reaction of 3 with CrCl 3 (THF) 3 resulted in the octahedral complex [(Ph 2 P) 2 C(H)C═N( t -Bu)O]CrCl 2 (THF) 2 ·0.5THF·0.5(toluene) ( 9 ). The complexation of ligand 4 with CrCl 3 (THF) 3 switched the connectivity to classical form and afforded the octahedral chromium complex [(Ph 2 P)C(H)C═N(2,6- i -Pr 2 C 6 H 3 )O]CrCl 2 (THF) 2 ·1.5THF ( 10 ). In contrast, the reaction of the classical ligand 5 with CrCl 3 (THF) 3 resulted in [(Ph 2 P)C(H)═P(Ph 2 )C═N(2,4,6-Me 3 C 6 H 2 )O]Cr(THF) 2 Cl 2 ( 11 ) with a nonclassical type of connectivity. Reaction of 11 with DEAC switched the connectivity back to a classical type, affording {(EtCl 2 Al)[(Ph 2 P) 2 C(H)C═N(2,4,6-Me 3 C 6 H 2 )OAlEt 2 ](μ-Cl)Cr} 2 (μ-Cl) 2 ·(toluene) ( 12 ). The catalytic behavior of all of these complexes has been assessed under different oligomerization conditions, and it was found that the modification of the DPPM framework with cumulenes considerably enhances their catalytic performance in comparison to catalysts 6 and 7 . In any event, a Schultz–Flory distribution of oligomers was obtained. However, the in situ catalytic testing of ligands 2 – 4 using Cr(acac) 3 as metal precursor and DMAO as cocatalyst, in methylcyclohexane, switched the catalytic behavior to selective formation of 1-hexene and 1-octene (no higher liquid oligomers) along with a significant amount of narrowly dispersed, low-molecular-weight polyethylene wax. Interestingly, the precatalyst 12 showed self-activating trimerization capability with moderate activity.