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Issue 2, 2012
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A phosphino-oxazoline ligand as a P,N-bridge in palladium/cobalt or P,N-chelate in nickel complexes: catalytic ethylene oligomerization

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Abstract

The Pd(II) complex [PdCl2(1)] [1 = ({oxazolin-2-yl}methyl)diphenylphosphine] was obtained by the 1 : 1 reaction of 1 with [PdCl2(NCPh)2]. Although this neutral complex is stable in the solid-state and in solution, it reacts with the dinuclear complex [CoCl2(μ-1)]2 to afford the heterometallic zwitterionic complex [{PdCl(1)}+(μ-1)(CoCl3)] (2). Under inert atmosphere, two equivalents of 1 reacted with [NiCl2(dme)] to give trans-[NiCl2(1)2] (3) in CH2Cl2 but cis-[NiCl2(1)2] (4) in CHCl3. When the latter reaction was performed in air, trans-[NiCl2(5)2] (6) [5 = ({oxazolin-2-yl}methyl)diphenylphosphine oxide] was obtained. All metal complexes, 2, 3, 4 and 6, have been structurally characterized by X-ray diffraction. Complexes 3, 4 and 6 have been evaluated as precatalysts for ethylene oligomerisation in the presence of AlEtCl2 as cocatalyst. Complexes 3 and 6 yielded a turnover frequency (TOF) of 60 700 and 62 600 mol of C2H4/((mol of Ni)·h), respectively, in the presence of 10 equiv. of AlEtCl2. In the presence of only 6 equiv. of cocatalyst, these Ni complexes yielded TOF values of 41 500 and 58 000 mol of C2H4/((mol of Ni)·h), respectively.

Graphical abstract: A phosphino-oxazoline ligand as a P,N-bridge in palladium/cobalt or P,N-chelate in nickel complexes: catalytic ethylene oligomerization

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Publication details

The article was received on 18 Jul 2011, accepted on 21 Sep 2011 and first published on 07 Nov 2011


Article type: Paper
DOI: 10.1039/C1DT11352F
Citation: Dalton Trans., 2012,41, 379-386
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    A phosphino-oxazoline ligand as a P,N-bridge in palladium/cobalt or P,N-chelate in nickel complexes: catalytic ethylene oligomerization

    S. Zhang, R. Pattacini, S. Jie and P. Braunstein, Dalton Trans., 2012, 41, 379
    DOI: 10.1039/C1DT11352F

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