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Issue 42, 2016
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Chromium complexes bearing amidinato-phosphino ligand: synthesis, characterization, and catalytic properties of ethylene tri-/tetramerization and polymerization

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Abstract

An amidinato-phosphino ligand ArN[double bond, length as m-dash]C(R)NH(o-Ph2PC6H4) (Ar = 2,4,6-Me3C6H2, R = Ph (1); Ar = 2,6-iPr2C6H3, R = Ph (2); Ar = 2,6-iPr2C6H3, R = tBu (3)) was prepared. The ligand reacted with CrCl3(THF)3 to yield the N,P-chelation complex [ArNHC(R)[double bond, length as m-dash]N(o-Ph2PC6H4)]CrCl3(THF) (4–6), and the ligand’s lithium salt ArN[double bond, length as m-dash]C(R)N(o-Ph2PC6H4)Li reacted with the respective CrCl3(THF)3 and CrCl2(THF)2 to give the N,N,P-chelation complexes [ArN[double bond, length as m-dash]C(R)N(o-Ph2PC6H4)]CrCl2(THF) (7–8) and {[ArN[double bond, length as m-dash]C(R)N(o-Ph2PC6H4)]Cr(μ-Cl)}2 (9–11). Complexes 1–11 were characterized by IR, NMR (for 1–3), EPR (for 4–11) spectroscopy and CHN elemental analysis, of which 3, 5, 8, and 11 were further studied by X-ray crystallography. Upon activation with an organoaluminum cocatalyst, complexes 4–6 were all catalytically active in ethylene tri-/tetramerization along with ethylene polymerization, and complexes 7–11 functioned as well but in ethylene polymerization. The correlation between the structure and the catalytic properties of the catalyst system is discussed.

Graphical abstract: Chromium complexes bearing amidinato-phosphino ligand: synthesis, characterization, and catalytic properties of ethylene tri-/tetramerization and polymerization

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Publication details

The article was received on 13 Aug 2016, accepted on 21 Sep 2016 and first published on 22 Sep 2016


Article type: Paper
DOI: 10.1039/C6DT03216H
Citation: Dalton Trans., 2016,45, 17020-17029
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    Chromium complexes bearing amidinato-phosphino ligand: synthesis, characterization, and catalytic properties of ethylene tri-/tetramerization and polymerization

    R. Liu, K. Zhu, X. Zhong, J. Li, Z. Liu, S. Chen and H. Zhu, Dalton Trans., 2016, 45, 17020
    DOI: 10.1039/C6DT03216H

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