Zirconium complexes incorporated with asymmetrical tridentate pincer type mono- and di-anionic pyrrolyl ligands: Mechanism and reactivity as catalytic precursors

Jia Wei Hsu, Yu Chun Lin, Ching Sheng Hsiao, Amitabha Datta, Chia Her Lin, Jui Hsien Huang, Jing Cherng Tsai, Wei Che Hsu

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Abstract

The reactions of Zr(NR 2) 4 (1, R = Me; 2, R = Et) with an asymmetrical tridentate pincer type pyrrole ligand precursor [C 4H 2NH(2-CH 2NH tBu)(5-CH 2NMe 2)] and treatment of the derivatives with either PhNCS or PhNCO have been carried out and characterized. Reacting Zr(NR 2) 4 (1, R = Me; 2, R = Et) with [C 4H 2NH(2-CH 2NH tBu)(5-CH 2NMe 2)] generates Zr[C 4H 2N(2-CH 2N tBu)(5-CH 2NMe 2)](NR 2) 2 (3, R = Me; 4, R = Et) in high yield along with the elimination of 2 equiv of dimethylamine or diethylamine, respectively. Interestingly, while changing the solvent from Et 2O to CH 2Cl 2, the complex Zr[C 4H 2N(2-CH 2N tBu)(5-CH 2NMe 2)][C 4H 2N(2-CH 2NH tBu)(5-CH 2NMe 2)]Cl (5) is produced by undergoing C-Cl bond cleavage. Furthermore, reaction of either 3 or 4 with 1 or 2 equiv of PhNCS or PhNCO yields Zr[C 4H 2N(2-CH 2N tBu)(5-CH 2NMe 2)](NMe 2)[PhNC(NMe 2)S] (6), Zr[C 4H 2N(2-CH 2N tBu)(5-CH 2NMe 2)](NEt 2)[PhNC(NEt 2)O] (7) and Zr[C 4H 2N(2-CH 2NH tBu)(5-CH 2NMe 2)][PhNC(NEt 2)O] 3 (8), respectively. All the aforementioned complexes were characterized by 1H and 13C NMR spectrometry and the molecular structures of 5, 6, and 8 have been determined by single-crystal X-ray diffractometry. Complexes 4, 5, and 7 initiated the ethylene polymerization in the presence of MAO as the co-catalyst.

Original languageEnglish
Pages (from-to)7700-7707
Number of pages8
JournalDalton Transactions
Volume41
Issue number25
DOIs
Publication statusPublished - 2012 Jul 7

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All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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