American Chemical Society
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Bimetallic Ethylene Tetramerization Catalysts Derived from Chiral DPPDME Ligands: Syntheses, Structural Characterizations, and Catalytic Performance of [(DPPDME)CrCl3]2 (DPPDME = S,S- and R,R-chiraphos and meso-achiraphos)

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posted on 2010-11-22, 00:00 authored by Sung-Kwan Kim, Tae-Jin Kim, Jae-Ho Chung, Tak-Kyu Hahn, Sung-Soek Chae, Ho-Seong Lee, Minserk Cheong, Sang Ook Kang
Chromium-based ethylene tetramerization catalyst precursors of the type {(DPPME)CrCl2(μ-Cl)}2 with a chiraphos ligand backbone [DPPME = {Ar(R1R2)}2PCH(CH3)CH(CH3)P{Ar(R1R2)}2] were prepared and characterized, in which substituents on the aryl phosphine varied with electron-donating and -withdrawing groups (S,S-ArR1 = H, R2 = H 1; R,R-ArR1 = H, R2 = H 2; meso-ArR1 = H, R2 = H 3; S,S-ArR1 = Me, R2 = H 4; S,S-ArR1 = OMe, R2 = H 5; S,S-ArR1 = H, R2 = Me 6; S,S-ArR1 = H, R2 = OMe 7; S,S-ArR1 = H, R2 = F 8). Depending on the coordination of chiraphos or achiraphos ligands, the corresponding bimetallic chromium complexes were prepared from the reaction of CrCl3(THF)3. S,S- and R,R-Chiraphos-based chromium metal complexes, 9 and 10, were crystallographically characterized to be dimeric, bridged by two chlorine ligands, whereas a meso achiraphos ligand resulted in a monomeric chromium complex, 17, when crystallized in acetonitrile. The observed average Cr−P bond distances of 9 [2.491(1) Å] and 10 [2.489(2) Å] were shorter than those found in 17 [2.512(1) Å]. The bite angles of 9 and 10 [79.45(6)° and 79.91(8)°] were also smaller than those of 17 [82.06(5)°]. Isolated chiraphos-based Cr(III) precursors, 916, exhibited enhanced ethylene tetramerization activities in the range 274−2,256 kg/g Cr/h when 30 bar of ethylene was engaged in the presence of MMAO-12A. Further, methyl substitution at the para-position of the phenyl group on the S,S-chiraphos ligand produced the expected chromium dimer, [CrCl2(μ-Cl){(P,P)-κ2-(S,S-DPPDME-6)}]2 (14), and exhibited higher catalytic performance, reaching a 1-octene activity of 2256 kg/g Cr/h with 51.1% selectivity at 45 °C. Further, temperature control at 25 °C increased 1-octene selectivity to 77.4% at the expense of reduced activity of 580 kg/g Cr/h. DFT calculations on the seven-membered metallacycle intermediates suggested stronger Cr−P bonding with a S,S-/R,R-chiraphos ligand backbone, and this interaction can be related to the enhanced catalytic performance.