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Reactions between an Ethylene Oligomerization Chromium(III) Precatalyst and Aluminum-Based Activators: Alkyl and Cationic Complexes with a Tridentate NPN Ligand
Liu, Shaofeng1,2,3; Pattacini, Roberto1; Braunstein, Pierre1
2011-07-11
Source PublicationORGANOMETALLICS
ISSN0276-7333
Volume30Issue:13Pages:3549-3558
AbstractTo gain a deeper knowledge of the nature of the species formed in situ by reaction of a catalyst precursor complex and typical cocatalysts used for ethylene oligomerization or polymerization, the Cr(III) complex fac-[Cr(NPN)Cl-3] (1; NPN = bis(2-picolyl)phenylphosphine) was reacted with MAO and partial methylation to give the mononuclear complex fac-[Cr(NPN)Cl2.23Me0.77] (2) was observed, whereas reaction with AlMe3 in toluene led to partial halide abstraction and produced the dinuclear, chloride-bridged dicationic complex [{fac-Cr(NPN)Me(mu-Cl)}(2)] [AlMexCl4-x](2) (3. [AlMexCl4-x]2), in which the metal centers are bridged by two chloride ligands. The complex fac-[Cr(NPN)Cl2Et] (4) was isolated in high yield from the reaction of 1 with AlEt3 and contains a rare example of Cr-III-Et function. Upon treatment of 1 with EtAlCl2, the dinuclear Cr(III) complex [{fac-Cr(NPN)}(2)(mu-Cl)(3)][AlCl4](3)center dot(5 center dot[AlCl4](3)) was obtained, which contains three bridging chlorides. Thus, under the conditions investigated, MAO and AlEt3 behaved as alkylation agents, whereas AlMe3 and EtAlCl2 reacted as cationization agents. On activation with MAO and under comparable conditions, 1-5 exhibited similar catalytic properties, with activities between 2700 and 2800 g of C2H4/((g of Cr) h), but the major oligomer produced using the 4/MAO system was 1-decene. The neutral alkyl complexes 2 and 4 and the cationic complexes 3 and 5 did not exhibit catalytic activity for ethylene oligomeriz,ation in the absence of MAO. The structures of the complexes 2, 3 [AlMeCl4-x](2), 4, and 5 center dot[AlCl4](3) have been determined by singlecrystal X-ray diffraction.
DOI10.1021/om200243a
Indexed BySCI
Language英语
WOS IDWOS:000292417900018
PublisherAMER CHEMICAL SOC
Citation statistics
Cited Times:26[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/72676
Collection中国科学院化学研究所
Corresponding AuthorBraunstein, Pierre
Affiliation1.Univ Strasbourg, Lab Chim Coordinat, Inst Chim, CNRS,UMR 7177, F-67081 Strasbourg, France
2.Chinese Acad Sci, Inst Chem, Key Lab Engn Plast, Beijing 100190, Peoples R China
3.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
Recommended Citation
GB/T 7714
Liu, Shaofeng,Pattacini, Roberto,Braunstein, Pierre. Reactions between an Ethylene Oligomerization Chromium(III) Precatalyst and Aluminum-Based Activators: Alkyl and Cationic Complexes with a Tridentate NPN Ligand[J]. ORGANOMETALLICS,2011,30(13):3549-3558.
APA Liu, Shaofeng,Pattacini, Roberto,&Braunstein, Pierre.(2011).Reactions between an Ethylene Oligomerization Chromium(III) Precatalyst and Aluminum-Based Activators: Alkyl and Cationic Complexes with a Tridentate NPN Ligand.ORGANOMETALLICS,30(13),3549-3558.
MLA Liu, Shaofeng,et al."Reactions between an Ethylene Oligomerization Chromium(III) Precatalyst and Aluminum-Based Activators: Alkyl and Cationic Complexes with a Tridentate NPN Ligand".ORGANOMETALLICS 30.13(2011):3549-3558.
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