Structural elucidation of tungsten compounds containing arylamine, piperazine and morpholine fragments of pyrrole and keto-amine ligands

Guan Xuan Chen, Amitabha Datta, Hung Chang Hsiao, Chia Her Lin, Jui-Hsien Huang

Research output: Contribution to journalArticle

Abstract

Various imido tungsten derivatives incorporating bidentate pyrrole-piperazine, pyrrole-morpholine, pyrrole-imine and keto-amine precursors were synthesized. Reacting W(=NtBu)2(NHtBu)2 with one equivalent of the pyrrole-phenylpiperazine ligand {C4H3NH-[2-CH2N(CH2CH2)2NPh]} in toluene generated [W(=NtBu)2(NHtBu){C4H3N-[2-CH2N(CH2CH2)2NPh]}] (1). Similarly, addition of W(=NtBu)2(NHtBu)2 to one equivalent of the pyrrole-morpholine ligand {C4H3NH-[2-CH2N(CH2CH2)2O]} in toluene afforded [W(=NtBu)2(NHtBu){C4H3N-[2-CH2N(CH2CH2)2O]}] (2), which was converted to [W(=NtBu)2{C4H3N-[2-CH2N(CH2CH2)2O]}]22-O) (3) in moisture. Reacting the pyrrole-imine ligand {C4H3NH-[2-CH=N(C6H3-2,6-iPr2)]} with one equivalent of W(=NtBu)2(NHtBu)2 in toluene gave [W(=NtBu)2(NHtBu){C4H3N-[2-CH=N(C6H3-2,6-iPr2)]}] (4), which was transformed to [W(=NtBu)(NHtBu){C4H3N-[2-CH=N(C6H3-2,6-iPr2)]}(μ-O)]2 (5) upon absorbing moisture. Furthermore, when one equivalent of {C4H3NH-[2-CH=NC2H4N(C2H4)2O]} reacted with W(=NtBu)2(NHtBu)2 in toluene, {W(=NtBu)2{C4H3N-[2-CH=NC2H4N(C2H4)2O]}2} (6) was isolated. The tungsten keto-amine compounds {W(=NtBu)2[OCMeCHCMeN(C6H3-2,6-iPr2)]2} (7) and {W(=NtBu)2[OCMeCHCMeNCH2CH2N(CH2CH2)2O]2} (8) were obtained by the reaction between W(=NtBu)2(NHtBu)2 and two equivalents of the corresponding keto-amine ligands in toluene. All the tungsten derivatives were characterized by 1H and 13C NMR spectroscopy. Single crystal X-ray diffraction analysis revealed that in compounds, 1, 3, 5, 6 and 7, the central W atom belonged to either a distorted trigonal bipyramidal or an octahedral geometrical arrangement. Overall, the influence of the substituted pyrrole and keto-amine bidentate precursors on the imido tungsten derivatives were explored and structurally constructed.

Original languageEnglish
Pages (from-to)299-305
Number of pages7
JournalPolyhedron
Volume101
DOIs
Publication statusPublished - 2015 Nov 24

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Tungsten Compounds
Tungsten compounds
tungsten compounds
Pyrroles
pyrroles
Amines
Toluene
amines
Ligands
fragments
Tungsten
toluene
ligands
methylidyne
tungsten
Derivatives
Imines
Moisture
moisture
imines

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Chen, Guan Xuan ; Datta, Amitabha ; Hsiao, Hung Chang ; Lin, Chia Her ; Huang, Jui-Hsien. / Structural elucidation of tungsten compounds containing arylamine, piperazine and morpholine fragments of pyrrole and keto-amine ligands. In: Polyhedron. 2015 ; Vol. 101. pp. 299-305.
@article{f6a214fdfaf34964b53772460c7a922b,
title = "Structural elucidation of tungsten compounds containing arylamine, piperazine and morpholine fragments of pyrrole and keto-amine ligands",
abstract = "Various imido tungsten derivatives incorporating bidentate pyrrole-piperazine, pyrrole-morpholine, pyrrole-imine and keto-amine precursors were synthesized. Reacting W(=NtBu)2(NHtBu)2 with one equivalent of the pyrrole-phenylpiperazine ligand {C4H3NH-[2-CH2N(CH2CH2)2NPh]} in toluene generated [W(=NtBu)2(NHtBu){C4H3N-[2-CH2N(CH2CH2)2NPh]}] (1). Similarly, addition of W(=NtBu)2(NHtBu)2 to one equivalent of the pyrrole-morpholine ligand {C4H3NH-[2-CH2N(CH2CH2)2O]} in toluene afforded [W(=NtBu)2(NHtBu){C4H3N-[2-CH2N(CH2CH2)2O]}] (2), which was converted to [W(=NtBu)2{C4H3N-[2-CH2N(CH2CH2)2O]}]2(μ2-O) (3) in moisture. Reacting the pyrrole-imine ligand {C4H3NH-[2-CH=N(C6H3-2,6-iPr2)]} with one equivalent of W(=NtBu)2(NHtBu)2 in toluene gave [W(=NtBu)2(NHtBu){C4H3N-[2-CH=N(C6H3-2,6-iPr2)]}] (4), which was transformed to [W(=NtBu)(NHtBu){C4H3N-[2-CH=N(C6H3-2,6-iPr2)]}(μ-O)]2 (5) upon absorbing moisture. Furthermore, when one equivalent of {C4H3NH-[2-CH=NC2H4N(C2H4)2O]} reacted with W(=NtBu)2(NHtBu)2 in toluene, {W(=NtBu)2{C4H3N-[2-CH=NC2H4N(C2H4)2O]}2} (6) was isolated. The tungsten keto-amine compounds {W(=NtBu)2[OCMeCHCMeN(C6H3-2,6-iPr2)]2} (7) and {W(=NtBu)2[OCMeCHCMeNCH2CH2N(CH2CH2)2O]2} (8) were obtained by the reaction between W(=NtBu)2(NHtBu)2 and two equivalents of the corresponding keto-amine ligands in toluene. All the tungsten derivatives were characterized by 1H and 13C NMR spectroscopy. Single crystal X-ray diffraction analysis revealed that in compounds, 1, 3, 5, 6 and 7, the central W atom belonged to either a distorted trigonal bipyramidal or an octahedral geometrical arrangement. Overall, the influence of the substituted pyrrole and keto-amine bidentate precursors on the imido tungsten derivatives were explored and structurally constructed.",
author = "Chen, {Guan Xuan} and Amitabha Datta and Hsiao, {Hung Chang} and Lin, {Chia Her} and Jui-Hsien Huang",
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language = "English",
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journal = "Polyhedron",
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Structural elucidation of tungsten compounds containing arylamine, piperazine and morpholine fragments of pyrrole and keto-amine ligands. / Chen, Guan Xuan; Datta, Amitabha; Hsiao, Hung Chang; Lin, Chia Her; Huang, Jui-Hsien.

In: Polyhedron, Vol. 101, 24.11.2015, p. 299-305.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Structural elucidation of tungsten compounds containing arylamine, piperazine and morpholine fragments of pyrrole and keto-amine ligands

AU - Chen, Guan Xuan

AU - Datta, Amitabha

AU - Hsiao, Hung Chang

AU - Lin, Chia Her

AU - Huang, Jui-Hsien

PY - 2015/11/24

Y1 - 2015/11/24

N2 - Various imido tungsten derivatives incorporating bidentate pyrrole-piperazine, pyrrole-morpholine, pyrrole-imine and keto-amine precursors were synthesized. Reacting W(=NtBu)2(NHtBu)2 with one equivalent of the pyrrole-phenylpiperazine ligand {C4H3NH-[2-CH2N(CH2CH2)2NPh]} in toluene generated [W(=NtBu)2(NHtBu){C4H3N-[2-CH2N(CH2CH2)2NPh]}] (1). Similarly, addition of W(=NtBu)2(NHtBu)2 to one equivalent of the pyrrole-morpholine ligand {C4H3NH-[2-CH2N(CH2CH2)2O]} in toluene afforded [W(=NtBu)2(NHtBu){C4H3N-[2-CH2N(CH2CH2)2O]}] (2), which was converted to [W(=NtBu)2{C4H3N-[2-CH2N(CH2CH2)2O]}]2(μ2-O) (3) in moisture. Reacting the pyrrole-imine ligand {C4H3NH-[2-CH=N(C6H3-2,6-iPr2)]} with one equivalent of W(=NtBu)2(NHtBu)2 in toluene gave [W(=NtBu)2(NHtBu){C4H3N-[2-CH=N(C6H3-2,6-iPr2)]}] (4), which was transformed to [W(=NtBu)(NHtBu){C4H3N-[2-CH=N(C6H3-2,6-iPr2)]}(μ-O)]2 (5) upon absorbing moisture. Furthermore, when one equivalent of {C4H3NH-[2-CH=NC2H4N(C2H4)2O]} reacted with W(=NtBu)2(NHtBu)2 in toluene, {W(=NtBu)2{C4H3N-[2-CH=NC2H4N(C2H4)2O]}2} (6) was isolated. The tungsten keto-amine compounds {W(=NtBu)2[OCMeCHCMeN(C6H3-2,6-iPr2)]2} (7) and {W(=NtBu)2[OCMeCHCMeNCH2CH2N(CH2CH2)2O]2} (8) were obtained by the reaction between W(=NtBu)2(NHtBu)2 and two equivalents of the corresponding keto-amine ligands in toluene. All the tungsten derivatives were characterized by 1H and 13C NMR spectroscopy. Single crystal X-ray diffraction analysis revealed that in compounds, 1, 3, 5, 6 and 7, the central W atom belonged to either a distorted trigonal bipyramidal or an octahedral geometrical arrangement. Overall, the influence of the substituted pyrrole and keto-amine bidentate precursors on the imido tungsten derivatives were explored and structurally constructed.

AB - Various imido tungsten derivatives incorporating bidentate pyrrole-piperazine, pyrrole-morpholine, pyrrole-imine and keto-amine precursors were synthesized. Reacting W(=NtBu)2(NHtBu)2 with one equivalent of the pyrrole-phenylpiperazine ligand {C4H3NH-[2-CH2N(CH2CH2)2NPh]} in toluene generated [W(=NtBu)2(NHtBu){C4H3N-[2-CH2N(CH2CH2)2NPh]}] (1). Similarly, addition of W(=NtBu)2(NHtBu)2 to one equivalent of the pyrrole-morpholine ligand {C4H3NH-[2-CH2N(CH2CH2)2O]} in toluene afforded [W(=NtBu)2(NHtBu){C4H3N-[2-CH2N(CH2CH2)2O]}] (2), which was converted to [W(=NtBu)2{C4H3N-[2-CH2N(CH2CH2)2O]}]2(μ2-O) (3) in moisture. Reacting the pyrrole-imine ligand {C4H3NH-[2-CH=N(C6H3-2,6-iPr2)]} with one equivalent of W(=NtBu)2(NHtBu)2 in toluene gave [W(=NtBu)2(NHtBu){C4H3N-[2-CH=N(C6H3-2,6-iPr2)]}] (4), which was transformed to [W(=NtBu)(NHtBu){C4H3N-[2-CH=N(C6H3-2,6-iPr2)]}(μ-O)]2 (5) upon absorbing moisture. Furthermore, when one equivalent of {C4H3NH-[2-CH=NC2H4N(C2H4)2O]} reacted with W(=NtBu)2(NHtBu)2 in toluene, {W(=NtBu)2{C4H3N-[2-CH=NC2H4N(C2H4)2O]}2} (6) was isolated. The tungsten keto-amine compounds {W(=NtBu)2[OCMeCHCMeN(C6H3-2,6-iPr2)]2} (7) and {W(=NtBu)2[OCMeCHCMeNCH2CH2N(CH2CH2)2O]2} (8) were obtained by the reaction between W(=NtBu)2(NHtBu)2 and two equivalents of the corresponding keto-amine ligands in toluene. All the tungsten derivatives were characterized by 1H and 13C NMR spectroscopy. Single crystal X-ray diffraction analysis revealed that in compounds, 1, 3, 5, 6 and 7, the central W atom belonged to either a distorted trigonal bipyramidal or an octahedral geometrical arrangement. Overall, the influence of the substituted pyrrole and keto-amine bidentate precursors on the imido tungsten derivatives were explored and structurally constructed.

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