Four- and five-coordinate aluminum ketiminate complexes: Synthesis, characterization, and ring-opening polymerization

Ru Ching Yu, Chen Hsiung Hung, Jui Hsien Huang, Horng Yi Lee, Jwu Ting Chen

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Abstract

A series of aluminum complexes featuring with the ketiminate ligand, OCMeCHCMeNHAr (Ar = 2,6-iPr2C6H3, 1), have been prepared and characterized spectroscopically and structurally. Reactions of 1 with trialkylaluminum in 1:1 or 1:2 molar ratio generate four- and five-coordinated aluminum complexes (OCMeCHCMeNAr)AlR2 (R = Me (2); R = Et (3)) and (OCMeCHCMeNAr)2AlR (R = Me (4); R = Et (5)) in high yields. Similarly, reaction of AlCl3 with 1 or 2 equiv of the lithiated 1 in toluene afforded bis(ketiminate) aluminum chloride complex, (OCMeCHCMeNAr)2AlCl (6) or (OCMeCHCMeNAr)AlCl2 (7). Surprisingly, reacting 6 with 1 equiv of AgBF4 in methylene/acetonitrile mixsolvents generates (OCMeCHCMeNAr)2AlF (8) in moderate yield. The structures of complexes 2-6 and 8 have been determined by X-ray crystallography. Complexes 2 and 3 both exhibit tetrahedron structures with the aluminum atom surrounded by oxygen and nitrogen atoms of chelating ketiminate and two alkyl groups. The mono- and bis-ketiminate aluminum complexes 2 - 5 have shown moderate activity toward the ring-opening polymerization of ε-caprolactone.

Original languageEnglish
Pages (from-to)6450-6455
Number of pages6
JournalInorganic Chemistry
Volume41
Issue number24
DOIs
Publication statusPublished - 2002 Dec 2

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Ring opening polymerization
Aluminum
polymerization
aluminum
rings
synthesis
aluminum chlorides
Atoms
X ray crystallography
Toluene
Chelation
methylene
tetrahedrons
nitrogen atoms
crystallography
acetonitrile
toluene
oxygen atoms
Nitrogen
Oxygen

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Yu, Ru Ching ; Hung, Chen Hsiung ; Huang, Jui Hsien ; Lee, Horng Yi ; Chen, Jwu Ting. / Four- and five-coordinate aluminum ketiminate complexes : Synthesis, characterization, and ring-opening polymerization. In: Inorganic Chemistry. 2002 ; Vol. 41, No. 24. pp. 6450-6455.
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abstract = "A series of aluminum complexes featuring with the ketiminate ligand, OCMeCHCMeNHAr (Ar = 2,6-iPr2C6H3, 1), have been prepared and characterized spectroscopically and structurally. Reactions of 1 with trialkylaluminum in 1:1 or 1:2 molar ratio generate four- and five-coordinated aluminum complexes (OCMeCHCMeNAr)AlR2 (R = Me (2); R = Et (3)) and (OCMeCHCMeNAr)2AlR (R = Me (4); R = Et (5)) in high yields. Similarly, reaction of AlCl3 with 1 or 2 equiv of the lithiated 1 in toluene afforded bis(ketiminate) aluminum chloride complex, (OCMeCHCMeNAr)2AlCl (6) or (OCMeCHCMeNAr)AlCl2 (7). Surprisingly, reacting 6 with 1 equiv of AgBF4 in methylene/acetonitrile mixsolvents generates (OCMeCHCMeNAr)2AlF (8) in moderate yield. The structures of complexes 2-6 and 8 have been determined by X-ray crystallography. Complexes 2 and 3 both exhibit tetrahedron structures with the aluminum atom surrounded by oxygen and nitrogen atoms of chelating ketiminate and two alkyl groups. The mono- and bis-ketiminate aluminum complexes 2 - 5 have shown moderate activity toward the ring-opening polymerization of ε-caprolactone.",
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Four- and five-coordinate aluminum ketiminate complexes : Synthesis, characterization, and ring-opening polymerization. / Yu, Ru Ching; Hung, Chen Hsiung; Huang, Jui Hsien; Lee, Horng Yi; Chen, Jwu Ting.

In: Inorganic Chemistry, Vol. 41, No. 24, 02.12.2002, p. 6450-6455.

Research output: Contribution to journalArticle

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T1 - Four- and five-coordinate aluminum ketiminate complexes

T2 - Synthesis, characterization, and ring-opening polymerization

AU - Yu, Ru Ching

AU - Hung, Chen Hsiung

AU - Huang, Jui Hsien

AU - Lee, Horng Yi

AU - Chen, Jwu Ting

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N2 - A series of aluminum complexes featuring with the ketiminate ligand, OCMeCHCMeNHAr (Ar = 2,6-iPr2C6H3, 1), have been prepared and characterized spectroscopically and structurally. Reactions of 1 with trialkylaluminum in 1:1 or 1:2 molar ratio generate four- and five-coordinated aluminum complexes (OCMeCHCMeNAr)AlR2 (R = Me (2); R = Et (3)) and (OCMeCHCMeNAr)2AlR (R = Me (4); R = Et (5)) in high yields. Similarly, reaction of AlCl3 with 1 or 2 equiv of the lithiated 1 in toluene afforded bis(ketiminate) aluminum chloride complex, (OCMeCHCMeNAr)2AlCl (6) or (OCMeCHCMeNAr)AlCl2 (7). Surprisingly, reacting 6 with 1 equiv of AgBF4 in methylene/acetonitrile mixsolvents generates (OCMeCHCMeNAr)2AlF (8) in moderate yield. The structures of complexes 2-6 and 8 have been determined by X-ray crystallography. Complexes 2 and 3 both exhibit tetrahedron structures with the aluminum atom surrounded by oxygen and nitrogen atoms of chelating ketiminate and two alkyl groups. The mono- and bis-ketiminate aluminum complexes 2 - 5 have shown moderate activity toward the ring-opening polymerization of ε-caprolactone.

AB - A series of aluminum complexes featuring with the ketiminate ligand, OCMeCHCMeNHAr (Ar = 2,6-iPr2C6H3, 1), have been prepared and characterized spectroscopically and structurally. Reactions of 1 with trialkylaluminum in 1:1 or 1:2 molar ratio generate four- and five-coordinated aluminum complexes (OCMeCHCMeNAr)AlR2 (R = Me (2); R = Et (3)) and (OCMeCHCMeNAr)2AlR (R = Me (4); R = Et (5)) in high yields. Similarly, reaction of AlCl3 with 1 or 2 equiv of the lithiated 1 in toluene afforded bis(ketiminate) aluminum chloride complex, (OCMeCHCMeNAr)2AlCl (6) or (OCMeCHCMeNAr)AlCl2 (7). Surprisingly, reacting 6 with 1 equiv of AgBF4 in methylene/acetonitrile mixsolvents generates (OCMeCHCMeNAr)2AlF (8) in moderate yield. The structures of complexes 2-6 and 8 have been determined by X-ray crystallography. Complexes 2 and 3 both exhibit tetrahedron structures with the aluminum atom surrounded by oxygen and nitrogen atoms of chelating ketiminate and two alkyl groups. The mono- and bis-ketiminate aluminum complexes 2 - 5 have shown moderate activity toward the ring-opening polymerization of ε-caprolactone.

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