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

doi:10.1039/c2dt30417a

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

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

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 language	English
Pages (from-to)	7700-7707
Number of pages	8
Journal	Dalton Transactions
Volume	41
Issue number	25
DOIs	https://doi.org/10.1039/c2dt30417a
Publication status	Published - 2012 Jul 7
Externally published	Yes

ASJC Scopus subject areas

Inorganic Chemistry

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10.1039/c2dt30417a

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@article{467e6d9383cf40389beb45e7a8eb3f98,

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

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.",

author = "Hsu, \{Jia Wei\} and Lin, \{Yu Chun\} and Hsiao, \{Ching Sheng\} and Amitabha Datta and Lin, \{Chia Her\} and Huang, \{Jui Hsien\} and Tsai, \{Jing Cherng\} and Hsu, \{Wei Che\}",

year = "2012",

month = jul,

day = "7",

doi = "10.1039/c2dt30417a",

language = "English",

volume = "41",

pages = "7700--7707",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "25",

}

TY - JOUR

T1 - Zirconium complexes incorporated with asymmetrical tridentate pincer type mono- and di-anionic pyrrolyl ligands

T2 - Mechanism and reactivity as catalytic precursors

AU - Hsu, Jia Wei

AU - Lin, Yu Chun

AU - Hsiao, Ching Sheng

AU - Datta, Amitabha

AU - Lin, Chia Her

AU - Huang, Jui Hsien

AU - Tsai, Jing Cherng

AU - Hsu, Wei Che

PY - 2012/7/7

Y1 - 2012/7/7

N2 - 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.

AB - 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.

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U2 - 10.1039/c2dt30417a

DO - 10.1039/c2dt30417a

M3 - Article

AN - SCOPUS:84862229604

SN - 1477-9226

VL - 41

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EP - 7707

JO - Dalton Transactions

JF - Dalton Transactions

IS - 25

ER -

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

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