Aluminum complexes incorporating symmetrical and asymmetrical tridentate pincer type pyrrolyl ligands: Synthesis, characterization and reactivity study

Pei Hsin Liu, Fu Jung Chuang, Cheng Yi Tu, Ching Han Hu, Tzu Wei Lin, Yu Tang Wang, Chia Her Lin, Amitabha Datta, Jui Hsien Huang

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Abstract

A series of aluminum complexes incorporating substituted symmetrical and asymmetrical tridentate pyrrolyl ligands are synthesized conveniently and the treatment of the derivatives with small organic molecules are analyzed. The reaction of lithiated [C4H2NH(2-CH2NH tBu)(5-CH2NR1R2)], where for 1, R1 = R2 = Me; 2, R1 = H, R2 = tBu, with AlCl3 in diethyl ether affords Al[C 4H2N(2-CH2NHtBu)(5-CH 2NMe2)]Cl2 (3) and Al[C4H 2N(2,5-CH2NHtBu)2]Cl2 (4), respectively, in high yields. Furthermore, subjecting 3 and 4 to reaction with one equiv. of LiNMePh in diethyl ether generates Al[C4H 2N(2-CH2NHtBu)(5-CH2NMe 2)][NMePh]Cl (5) and Al[C4H2N(2,5-CH 2NHtBu)2][NMePh]Cl (6), respectively, while eliminating one equiv. of LiCl. The reaction between compound 4 with two equiv. of LiO-Ph-4-Me in diethyl ether yields the aluminum di-phenoxide compound Al[C4H2N(2,5-CH2NHtBu) 2](O-Ph-4-Me)2 (7) whereas the combination of 3 and two equiv. of LiNHtBu, produces Al[C4H2N(2-CH 2NtBu)(5-CH2NMe2)](NH tBu)(NH2tBu) (8). Additionally, the mixing of 1 and one equiv. of AlMe3 renders Al[C4H 2N(2-CH2NHtBu)(5-CH2NMe 2)]Me2 (9). Adding one more equiv. of AlMe3 with 9 affords {Al[C4H2N(2-CH2NH tBu)(5-CH2NMe2)AlMe3]Me 2} (10), which can also be obtained by treating 1 with two equiv. of AlMe3 directly. The treatment of 9 with one equiv. of 2,6-dimethylphenol in diethyl ether gives the aluminum alkoxide derivative, Al[C4H2N(2-CH2NHtBu)(5-CH 2NMe2)](O-C6H3-2,6-Me 2)Me (11). Furthermore, the reaction between 9 and one equiv. of 1-ethyl-1-phenyl ketene, initiates the aluminum dimethyl complex Al{C 4H2N[2-CH2CEtPh-C(O)-NHtBu](5- CH2NMe2)}Me2 (12) with a C-N bond breakage and a C-C bond formation. All the Al-derivatives are characterized by 1H and 13C NMR spectroscopy and the molecular structures are determined by single crystal X-ray diffractometry in solid state.

Original languageEnglish
Pages (from-to)13754-13764
Number of pages11
JournalDalton Transactions
Volume42
Issue number37
DOIs
Publication statusPublished - 2013 Oct 7

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Aluminum
Ether
Ligands
Derivatives
X ray diffraction analysis
Molecular structure
Nuclear magnetic resonance spectroscopy
Single crystals
Molecules

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Liu, Pei Hsin ; Chuang, Fu Jung ; Tu, Cheng Yi ; Hu, Ching Han ; Lin, Tzu Wei ; Wang, Yu Tang ; Lin, Chia Her ; Datta, Amitabha ; Huang, Jui Hsien. / Aluminum complexes incorporating symmetrical and asymmetrical tridentate pincer type pyrrolyl ligands : Synthesis, characterization and reactivity study. In: Dalton Transactions. 2013 ; Vol. 42, No. 37. pp. 13754-13764.
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title = "Aluminum complexes incorporating symmetrical and asymmetrical tridentate pincer type pyrrolyl ligands: Synthesis, characterization and reactivity study",
abstract = "A series of aluminum complexes incorporating substituted symmetrical and asymmetrical tridentate pyrrolyl ligands are synthesized conveniently and the treatment of the derivatives with small organic molecules are analyzed. The reaction of lithiated [C4H2NH(2-CH2NH tBu)(5-CH2NR1R2)], where for 1, R1 = R2 = Me; 2, R1 = H, R2 = tBu, with AlCl3 in diethyl ether affords Al[C 4H2N(2-CH2NHtBu)(5-CH 2NMe2)]Cl2 (3) and Al[C4H 2N(2,5-CH2NHtBu)2]Cl2 (4), respectively, in high yields. Furthermore, subjecting 3 and 4 to reaction with one equiv. of LiNMePh in diethyl ether generates Al[C4H 2N(2-CH2NHtBu)(5-CH2NMe 2)][NMePh]Cl (5) and Al[C4H2N(2,5-CH 2NHtBu)2][NMePh]Cl (6), respectively, while eliminating one equiv. of LiCl. The reaction between compound 4 with two equiv. of LiO-Ph-4-Me in diethyl ether yields the aluminum di-phenoxide compound Al[C4H2N(2,5-CH2NHtBu) 2](O-Ph-4-Me)2 (7) whereas the combination of 3 and two equiv. of LiNHtBu, produces Al[C4H2N(2-CH 2NtBu)(5-CH2NMe2)](NH tBu)(NH2tBu) (8). Additionally, the mixing of 1 and one equiv. of AlMe3 renders Al[C4H 2N(2-CH2NHtBu)(5-CH2NMe 2)]Me2 (9). Adding one more equiv. of AlMe3 with 9 affords {Al[C4H2N(2-CH2NH tBu)(5-CH2NMe2)AlMe3]Me 2} (10), which can also be obtained by treating 1 with two equiv. of AlMe3 directly. The treatment of 9 with one equiv. of 2,6-dimethylphenol in diethyl ether gives the aluminum alkoxide derivative, Al[C4H2N(2-CH2NHtBu)(5-CH 2NMe2)](O-C6H3-2,6-Me 2)Me (11). Furthermore, the reaction between 9 and one equiv. of 1-ethyl-1-phenyl ketene, initiates the aluminum dimethyl complex Al{C 4H2N[2-CH2CEtPh-C(O)-NHtBu](5- CH2NMe2)}Me2 (12) with a C-N bond breakage and a C-C bond formation. All the Al-derivatives are characterized by 1H and 13C NMR spectroscopy and the molecular structures are determined by single crystal X-ray diffractometry in solid state.",
author = "Liu, {Pei Hsin} and Chuang, {Fu Jung} and Tu, {Cheng Yi} and Hu, {Ching Han} and Lin, {Tzu Wei} and Wang, {Yu Tang} and Lin, {Chia Her} and Amitabha Datta and Huang, {Jui Hsien}",
year = "2013",
month = "10",
day = "7",
doi = "10.1039/c3dt51133b",
language = "English",
volume = "42",
pages = "13754--13764",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "37",

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Aluminum complexes incorporating symmetrical and asymmetrical tridentate pincer type pyrrolyl ligands : Synthesis, characterization and reactivity study. / Liu, Pei Hsin; Chuang, Fu Jung; Tu, Cheng Yi; Hu, Ching Han; Lin, Tzu Wei; Wang, Yu Tang; Lin, Chia Her; Datta, Amitabha; Huang, Jui Hsien.

In: Dalton Transactions, Vol. 42, No. 37, 07.10.2013, p. 13754-13764.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Aluminum complexes incorporating symmetrical and asymmetrical tridentate pincer type pyrrolyl ligands

T2 - Synthesis, characterization and reactivity study

AU - Liu, Pei Hsin

AU - Chuang, Fu Jung

AU - Tu, Cheng Yi

AU - Hu, Ching Han

AU - Lin, Tzu Wei

AU - Wang, Yu Tang

AU - Lin, Chia Her

AU - Datta, Amitabha

AU - Huang, Jui Hsien

PY - 2013/10/7

Y1 - 2013/10/7

N2 - A series of aluminum complexes incorporating substituted symmetrical and asymmetrical tridentate pyrrolyl ligands are synthesized conveniently and the treatment of the derivatives with small organic molecules are analyzed. The reaction of lithiated [C4H2NH(2-CH2NH tBu)(5-CH2NR1R2)], where for 1, R1 = R2 = Me; 2, R1 = H, R2 = tBu, with AlCl3 in diethyl ether affords Al[C 4H2N(2-CH2NHtBu)(5-CH 2NMe2)]Cl2 (3) and Al[C4H 2N(2,5-CH2NHtBu)2]Cl2 (4), respectively, in high yields. Furthermore, subjecting 3 and 4 to reaction with one equiv. of LiNMePh in diethyl ether generates Al[C4H 2N(2-CH2NHtBu)(5-CH2NMe 2)][NMePh]Cl (5) and Al[C4H2N(2,5-CH 2NHtBu)2][NMePh]Cl (6), respectively, while eliminating one equiv. of LiCl. The reaction between compound 4 with two equiv. of LiO-Ph-4-Me in diethyl ether yields the aluminum di-phenoxide compound Al[C4H2N(2,5-CH2NHtBu) 2](O-Ph-4-Me)2 (7) whereas the combination of 3 and two equiv. of LiNHtBu, produces Al[C4H2N(2-CH 2NtBu)(5-CH2NMe2)](NH tBu)(NH2tBu) (8). Additionally, the mixing of 1 and one equiv. of AlMe3 renders Al[C4H 2N(2-CH2NHtBu)(5-CH2NMe 2)]Me2 (9). Adding one more equiv. of AlMe3 with 9 affords {Al[C4H2N(2-CH2NH tBu)(5-CH2NMe2)AlMe3]Me 2} (10), which can also be obtained by treating 1 with two equiv. of AlMe3 directly. The treatment of 9 with one equiv. of 2,6-dimethylphenol in diethyl ether gives the aluminum alkoxide derivative, Al[C4H2N(2-CH2NHtBu)(5-CH 2NMe2)](O-C6H3-2,6-Me 2)Me (11). Furthermore, the reaction between 9 and one equiv. of 1-ethyl-1-phenyl ketene, initiates the aluminum dimethyl complex Al{C 4H2N[2-CH2CEtPh-C(O)-NHtBu](5- CH2NMe2)}Me2 (12) with a C-N bond breakage and a C-C bond formation. All the Al-derivatives are characterized by 1H and 13C NMR spectroscopy and the molecular structures are determined by single crystal X-ray diffractometry in solid state.

AB - A series of aluminum complexes incorporating substituted symmetrical and asymmetrical tridentate pyrrolyl ligands are synthesized conveniently and the treatment of the derivatives with small organic molecules are analyzed. The reaction of lithiated [C4H2NH(2-CH2NH tBu)(5-CH2NR1R2)], where for 1, R1 = R2 = Me; 2, R1 = H, R2 = tBu, with AlCl3 in diethyl ether affords Al[C 4H2N(2-CH2NHtBu)(5-CH 2NMe2)]Cl2 (3) and Al[C4H 2N(2,5-CH2NHtBu)2]Cl2 (4), respectively, in high yields. Furthermore, subjecting 3 and 4 to reaction with one equiv. of LiNMePh in diethyl ether generates Al[C4H 2N(2-CH2NHtBu)(5-CH2NMe 2)][NMePh]Cl (5) and Al[C4H2N(2,5-CH 2NHtBu)2][NMePh]Cl (6), respectively, while eliminating one equiv. of LiCl. The reaction between compound 4 with two equiv. of LiO-Ph-4-Me in diethyl ether yields the aluminum di-phenoxide compound Al[C4H2N(2,5-CH2NHtBu) 2](O-Ph-4-Me)2 (7) whereas the combination of 3 and two equiv. of LiNHtBu, produces Al[C4H2N(2-CH 2NtBu)(5-CH2NMe2)](NH tBu)(NH2tBu) (8). Additionally, the mixing of 1 and one equiv. of AlMe3 renders Al[C4H 2N(2-CH2NHtBu)(5-CH2NMe 2)]Me2 (9). Adding one more equiv. of AlMe3 with 9 affords {Al[C4H2N(2-CH2NH tBu)(5-CH2NMe2)AlMe3]Me 2} (10), which can also be obtained by treating 1 with two equiv. of AlMe3 directly. The treatment of 9 with one equiv. of 2,6-dimethylphenol in diethyl ether gives the aluminum alkoxide derivative, Al[C4H2N(2-CH2NHtBu)(5-CH 2NMe2)](O-C6H3-2,6-Me 2)Me (11). Furthermore, the reaction between 9 and one equiv. of 1-ethyl-1-phenyl ketene, initiates the aluminum dimethyl complex Al{C 4H2N[2-CH2CEtPh-C(O)-NHtBu](5- CH2NMe2)}Me2 (12) with a C-N bond breakage and a C-C bond formation. All the Al-derivatives are characterized by 1H and 13C NMR spectroscopy and the molecular structures are determined by single crystal X-ray diffractometry in solid state.

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