Anionic lanthanide complexes supported by a pyrrole-based tetradentate Schiff base ligand: Synthesis, structures and catalytic activity toward the polymerization of -caprolactone

Xue Qing Zhang; Miao Shui Lin; Bin Hu; Wen Qian Chen; Li Na Zheng; Jian Wu; Yan Mei Chen; Feng Ying Zhou; Ya Hong Li; Wu Li

doi:10.1016/j.poly.2011.11.029

Anionic lanthanide complexes supported by a pyrrole-based tetradentate Schiff base ligand: Synthesis, structures and catalytic activity toward the polymerization of -caprolactone

Xue Qing Zhang, Miao Shui Lin, Bin Hu, Wen Qian Chen, Li Na Zheng, Jian Wu, Yan Mei Chen, Feng Ying Zhou, Ya Hong Li, Wu Li

Advanced Institute for Materials Research (AIMR)

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

12 Citations (Scopus)

Abstract

The synthesis of the anionic organolanthanide complexes supported by H ₂bppda (H ₂bppda = N,N′-bis(2-pyrrylmethylidene)-1,2- phenylenediamine) ligand via different synthetic strategies is reported. Treatment of 1:4 mixture of LnCl ₃(THF) ₃ and LiN(SiMe ₃) ₂ with 2 equivalents of H ₂bppda in THF gave complexes of the formula [Li(THF) ₄][Ln(bppda) ₂]·THF (Ln = Nd (1·THF), Sm (2·THF), Gd (3·THF), Dy (4·THF), Er (5·THF)) and [Li(THF) ₅][Yb(bppda) ₂] (6). Reaction of Nd(BH ₄) ₃(THF) ₃ with 2 equivalents of Na ₂bppda in THF generated [Na(THF) ₆][Nd(bppda) ₂] (7) in good yield. Treatment of 1·THF with 1 equivalent of CoCp ₂ in THF led to the isolation of [CoCp ₂][Nd(bppda) ₂] (8). All of the complexes have been characterized by single crystal X-ray diffraction and elemental analyses. Complexes 1·THF-5·THF are isomorphous and isostructural, and the geometry of the octa-coordinated Ln ³⁺ ion in [Ln(bppda) ₂] ^- unit in these complexes is well described as either distorted dodecahedron or distorted bicapped trigonal prism. Lanthanide contraction was observed in 1·THF-5·THF and 6. The structures of complexes 1·THF, 7 and 8 are different from each other due to the variation of the cationic ions. The ring-opening polymerization reaction of -caprolactone initiated by 1·THF was conducted; it showed good activity.

Original language	English
Pages (from-to)	273-279
Number of pages	7
Journal	Polyhedron
Volume	33
Issue number	1
DOIs	https://doi.org/10.1016/j.poly.2011.11.029
Publication status	Published - 2012 Feb 9

Keywords

Anionic
Crystal structure
Lanthanide
Polymerization
Synthesis

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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Zhang, X. Q., Lin, M. S., Hu, B., Chen, W. Q., Zheng, L. N., Wu, J., Chen, Y. M., Zhou, F. Y., Li, Y. H., & Li, W. (2012). Anionic lanthanide complexes supported by a pyrrole-based tetradentate Schiff base ligand: Synthesis, structures and catalytic activity toward the polymerization of -caprolactone. Polyhedron, 33(1), 273-279. https://doi.org/10.1016/j.poly.2011.11.029

Anionic lanthanide complexes supported by a pyrrole-based tetradentate Schiff base ligand : Synthesis, structures and catalytic activity toward the polymerization of -caprolactone. / Zhang, Xue Qing; Lin, Miao Shui; Hu, Bin; Chen, Wen Qian; Zheng, Li Na; Wu, Jian; Chen, Yan Mei; Zhou, Feng Ying; Li, Ya Hong; Li, Wu.

In: Polyhedron, Vol. 33, No. 1, 09.02.2012, p. 273-279.

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

Zhang, Xue Qing ; Lin, Miao Shui ; Hu, Bin ; Chen, Wen Qian ; Zheng, Li Na ; Wu, Jian ; Chen, Yan Mei ; Zhou, Feng Ying ; Li, Ya Hong ; Li, Wu. / Anionic lanthanide complexes supported by a pyrrole-based tetradentate Schiff base ligand : Synthesis, structures and catalytic activity toward the polymerization of -caprolactone. In: Polyhedron. 2012 ; Vol. 33, No. 1. pp. 273-279.

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title = "Anionic lanthanide complexes supported by a pyrrole-based tetradentate Schiff base ligand: Synthesis, structures and catalytic activity toward the polymerization of -caprolactone",

abstract = "The synthesis of the anionic organolanthanide complexes supported by H 2bppda (H 2bppda = N,N′-bis(2-pyrrylmethylidene)-1,2- phenylenediamine) ligand via different synthetic strategies is reported. Treatment of 1:4 mixture of LnCl 3(THF) 3 and LiN(SiMe 3) 2 with 2 equivalents of H 2bppda in THF gave complexes of the formula [Li(THF) 4][Ln(bppda) 2]·THF (Ln = Nd (1·THF), Sm (2·THF), Gd (3·THF), Dy (4·THF), Er (5·THF)) and [Li(THF) 5][Yb(bppda) 2] (6). Reaction of Nd(BH 4) 3(THF) 3 with 2 equivalents of Na 2bppda in THF generated [Na(THF) 6][Nd(bppda) 2] (7) in good yield. Treatment of 1·THF with 1 equivalent of CoCp 2 in THF led to the isolation of [CoCp 2][Nd(bppda) 2] (8). All of the complexes have been characterized by single crystal X-ray diffraction and elemental analyses. Complexes 1·THF-5·THF are isomorphous and isostructural, and the geometry of the octa-coordinated Ln 3+ ion in [Ln(bppda) 2] - unit in these complexes is well described as either distorted dodecahedron or distorted bicapped trigonal prism. Lanthanide contraction was observed in 1·THF-5·THF and 6. The structures of complexes 1·THF, 7 and 8 are different from each other due to the variation of the cationic ions. The ring-opening polymerization reaction of -caprolactone initiated by 1·THF was conducted; it showed good activity.",

keywords = "Anionic, Crystal structure, Lanthanide, Polymerization, Synthesis",

author = "Zhang, {Xue Qing} and Lin, {Miao Shui} and Bin Hu and Chen, {Wen Qian} and Zheng, {Li Na} and Jian Wu and Chen, {Yan Mei} and Zhou, {Feng Ying} and Li, {Ya Hong} and Wu Li",

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T2 - Synthesis, structures and catalytic activity toward the polymerization of -caprolactone

AU - Zhang, Xue Qing

AU - Lin, Miao Shui

AU - Hu, Bin

AU - Chen, Wen Qian

AU - Zheng, Li Na

AU - Wu, Jian

AU - Chen, Yan Mei

AU - Zhou, Feng Ying

AU - Li, Ya Hong

AU - Li, Wu

PY - 2012/2/9

Y1 - 2012/2/9

N2 - The synthesis of the anionic organolanthanide complexes supported by H 2bppda (H 2bppda = N,N′-bis(2-pyrrylmethylidene)-1,2- phenylenediamine) ligand via different synthetic strategies is reported. Treatment of 1:4 mixture of LnCl 3(THF) 3 and LiN(SiMe 3) 2 with 2 equivalents of H 2bppda in THF gave complexes of the formula [Li(THF) 4][Ln(bppda) 2]·THF (Ln = Nd (1·THF), Sm (2·THF), Gd (3·THF), Dy (4·THF), Er (5·THF)) and [Li(THF) 5][Yb(bppda) 2] (6). Reaction of Nd(BH 4) 3(THF) 3 with 2 equivalents of Na 2bppda in THF generated [Na(THF) 6][Nd(bppda) 2] (7) in good yield. Treatment of 1·THF with 1 equivalent of CoCp 2 in THF led to the isolation of [CoCp 2][Nd(bppda) 2] (8). All of the complexes have been characterized by single crystal X-ray diffraction and elemental analyses. Complexes 1·THF-5·THF are isomorphous and isostructural, and the geometry of the octa-coordinated Ln 3+ ion in [Ln(bppda) 2] - unit in these complexes is well described as either distorted dodecahedron or distorted bicapped trigonal prism. Lanthanide contraction was observed in 1·THF-5·THF and 6. The structures of complexes 1·THF, 7 and 8 are different from each other due to the variation of the cationic ions. The ring-opening polymerization reaction of -caprolactone initiated by 1·THF was conducted; it showed good activity.

AB - The synthesis of the anionic organolanthanide complexes supported by H 2bppda (H 2bppda = N,N′-bis(2-pyrrylmethylidene)-1,2- phenylenediamine) ligand via different synthetic strategies is reported. Treatment of 1:4 mixture of LnCl 3(THF) 3 and LiN(SiMe 3) 2 with 2 equivalents of H 2bppda in THF gave complexes of the formula [Li(THF) 4][Ln(bppda) 2]·THF (Ln = Nd (1·THF), Sm (2·THF), Gd (3·THF), Dy (4·THF), Er (5·THF)) and [Li(THF) 5][Yb(bppda) 2] (6). Reaction of Nd(BH 4) 3(THF) 3 with 2 equivalents of Na 2bppda in THF generated [Na(THF) 6][Nd(bppda) 2] (7) in good yield. Treatment of 1·THF with 1 equivalent of CoCp 2 in THF led to the isolation of [CoCp 2][Nd(bppda) 2] (8). All of the complexes have been characterized by single crystal X-ray diffraction and elemental analyses. Complexes 1·THF-5·THF are isomorphous and isostructural, and the geometry of the octa-coordinated Ln 3+ ion in [Ln(bppda) 2] - unit in these complexes is well described as either distorted dodecahedron or distorted bicapped trigonal prism. Lanthanide contraction was observed in 1·THF-5·THF and 6. The structures of complexes 1·THF, 7 and 8 are different from each other due to the variation of the cationic ions. The ring-opening polymerization reaction of -caprolactone initiated by 1·THF was conducted; it showed good activity.

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KW - Lanthanide

KW - Polymerization

KW - Synthesis

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