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2D-QSPR/DFT studies of aryl-substituted PNP-Cr-based catalyst systems for highly selective ethylene oligomerization

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Abstract

1-Hexene and 1-octene are important comonomers for the synthesis of high performance polyolefins. Recently, various N-substituted Cr-bis(diphenylphosphino)amine (PNP-Cr) catalysts show the potential as excellent candidates for highly selective ethylene trimerization/tetramerization. In this work, a series of aryl-substituted PNP-Cr catalysts were studied by two-dimensional quantitative structure–property relationship (QSPR) method based on density functional theory (DFT) calculations. The heuristic method (HM) and best multi-linear regression (BMLR) were used to establish the best linear regression models to describe the relationship between selectivities and catalyst structures. Both Cr(I) and Cr(II) active site models for ethylene trimerization/tetramerization were considered. It was found that 1) the relativity and stability of the models were increased by using self-defined descriptors based on DFT calculations; 2) Cr(I)/Cr(III) centers were the most plausible active sites for ethylene trimerization, while Cr(II)/Cr(IV) active sites were most possibly responsible for ethylene tetramerization; and 3) the skeleton structures of the PNP-Cr system with good complanation and symmetry were crucial for achieving excellent catalytic selectivity of 1-octene, while the PNP-Cr backbone with a large steric effect on N atom would benefit ethylene trimerization. Six new PNP ligands with high selectivity toward ethylene trimerization/tetramerization were predicted based on descriptor analysis and the best linear regression models providing a good basis for further development of novel catalyst systems with better performance.

Aryl-substituted PNP-Cr-based catalyst systems

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Acknowledgments

This work is financially supported by the National Natural Science Foundation of China (21174037, 21004020), Program of Introducing Talents of Discipline to Universities (B08021) and Fundamental Research Funds for the Central Universities.

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  1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai, 200237, People’s Republic of China

    Siyang Tang, Zhen Liu, Xingwen Zhan, Ruihua Cheng, Xuelian He & Boping Liu

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  1. Siyang Tang
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  2. Zhen Liu
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Correspondence to Zhen Liu or Boping Liu.

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Tang, S., Liu, Z., Zhan, X. et al. 2D-QSPR/DFT studies of aryl-substituted PNP-Cr-based catalyst systems for highly selective ethylene oligomerization. J Mol Model 20, 2129 (2014). https://doi.org/10.1007/s00894-014-2129-4

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