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Issue 4, 2014
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Ni(II) tetraphosphine complexes as catalysts/initiators in the ring opening polymerization of ε-caprolactone

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Abstract

Reactions of the tetraphosphine ligand N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine) (dppeda) or 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) with NiCl2, ancillary ligand (C2H5)2NCS2Na (Na(dtc)) and NH4PF6 afforded two binuclear complexes [(dtc)Ni(dppeda)Ni(dtc)](PF6)2 (1) and [(dtc)Ni(dpppda)Ni(dtc)](PF6)2 (2). Compounds 1 and 2 were characterized by elemental analyses, IR spectra, 1H, 13C{1H} NMR and 31P{1H} NMR, electrospray ionization (ESI) mass spectra, thermogravimetric (TGA) experiments and single crystal X-ray diffraction. The Ni(II) atoms in both compounds form a square planar coordination geometry while the ligands hold a similar end-to-end coordination mode. Both products can catalyze the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) while 1 exhibited a higher catalytic activity than 2. Influencing aspects such as solvent, temperature, the ratio of ε-CL to catalyst, the presence of benzyl alcohol, concentration of ε-CL and reaction intervals were investigated.

Graphical abstract: Ni(ii) tetraphosphine complexes as catalysts/initiators in the ring opening polymerization of ε-caprolactone

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Publication details

The article was received on 02 Sep 2013, accepted on 11 Oct 2013 and first published on 11 Oct 2013


Article type: Paper
DOI: 10.1039/C3DT52412D
Citation: Dalton Trans., 2014,43, 1716-1723

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    Ni(II) tetraphosphine complexes as catalysts/initiators in the ring opening polymerization of ε-caprolactone

    X. Wu, Z. Ren and J. Lang, Dalton Trans., 2014, 43, 1716
    DOI: 10.1039/C3DT52412D

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