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

doi:10.1016/j.poly.2015.09.035

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^*

^*Corresponding author for this work

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

3 Citations (Scopus)

Abstract

Various imido tungsten derivatives incorporating bidentate pyrrole-piperazine, pyrrole-morpholine, pyrrole-imine and keto-amine precursors were synthesized. Reacting W(=N^tBu)₂(NH^tBu)₂ with one equivalent of the pyrrole-phenylpiperazine ligand {C₄H₃NH-[2-CH₂N(CH₂CH₂)₂NPh]} in toluene generated [W(=N^tBu)₂(NH^tBu){C₄H₃N-[2-CH₂N(CH₂CH₂)₂NPh]}] (1). Similarly, addition of W(=N^tBu)₂(NH^tBu)₂ to one equivalent of the pyrrole-morpholine ligand {C₄H₃NH-[2-CH₂N(CH₂CH₂)₂O]} in toluene afforded [W(=N^tBu)₂(NH^tBu){C₄H₃N-[2-CH₂N(CH₂CH₂)₂O]}] (2), which was converted to [W(=N^tBu)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(=N^tBu)₂(NH^tBu)₂ in toluene gave [W(=N^tBu)₂(NH^tBu){C₄H₃N-[2-CH=N(C₆H₃-2,6-ⁱPr₂)]}] (4), which was transformed to [W(=N^tBu)(NH^tBu){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(=N^tBu)₂(NH^tBu)₂ in toluene, {W(=N^tBu)₂{C₄H₃N-[2-CH=NC₂H₄N(C₂H₄)₂O]}₂} (6) was isolated. The tungsten keto-amine compounds {W(=N^tBu)₂[OCMeCHCMeN(C₆H₃-2,6-ⁱPr₂)]₂} (7) and {W(=N^tBu)₂[OCMeCHCMeNCH₂CH₂N(CH₂CH₂)₂O]₂} (8) were obtained by the reaction between W(=N^tBu)₂(NH^tBu)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 language	English
Pages (from-to)	299-305
Number of pages	7
Journal	Polyhedron
Volume	101
DOIs	https://doi.org/10.1016/j.poly.2015.09.035
Publication status	Published - 2015 Nov 24
Externally published	Yes

Keywords

Keto-amine
Morpholine
Piperazine
Pyrrole
Tungsten imido

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.poly.2015.09.035

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@article{327a36892fc444b89dde6fbb11f74dc2,

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.",

keywords = "Keto-amine, Morpholine, Piperazine, Pyrrole, Tungsten imido",

author = "Chen, {Guan Xuan} and Amitabha Datta and Hsiao, {Hung Chang} and Lin, {Chia Her} and Huang, {Jui Hsien}",

year = "2015",

month = nov,

day = "24",

doi = "10.1016/j.poly.2015.09.035",

language = "English",

volume = "101",

pages = "299--305",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Limited",

}

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.

KW - Keto-amine

KW - Morpholine

KW - Piperazine

KW - Pyrrole

KW - Tungsten imido

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U2 - 10.1016/j.poly.2015.09.035

DO - 10.1016/j.poly.2015.09.035

M3 - Article

AN - SCOPUS:84947438157

SN - 0277-5387

VL - 101

SP - 299

EP - 305

JO - Polyhedron

JF - Polyhedron

ER -

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

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Keywords

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