Niobium(V) Alkoxides. Synthesis, Structure, and Characterization of [Nb(μ-OCH2CH3)(OCH2C(CH3) 3)4]2, {[H3CC(CH2O)(CH2-μ-O)(C(O) 2)]Nb2(μ-O)(OCH2CH3) 5}2

Timothy J. Boyle; Todd M. Alam; Duane Dimos; Gregorio J. Moore; Catherine D. Buchheit; Husam N. Al-Shareef; Eric R. Mechenbier; Blakely R. Bear; Joseph W. Ziller

doi:10.1021/cm970506p

Niobium(V) Alkoxides. Synthesis, Structure, and Characterization of [Nb(μ-OCH₂CH₃)(OCH₂C(CH₃) ₃)₄]₂, {[H₃CC(CH₂O)(CH₂-μ-O)(C(O) ₂)]Nb₂(μ-O)(OCH₂CH₃) ₅}₂

Timothy J. Boyle^*, Todd M. Alam, Duane Dimos, Gregorio J. Moore, Catherine D. Buchheit, Husam N. Al-Shareef, Eric R. Mechenbier, Blakely R. Bear, Joseph W. Ziller

^*Corresponding author for this work

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Abstract

We have synthesized and isolated a number of unique niobium alkoxide compounds and introduced them into novel solution processes for the production of lead magnesium niobate oxide (PMN) and niobium-doped lead zirconate titanate oxide (PNZT) materials. A more sterically demanding analogue to Nb(OEt)₅ (Et = CH₂CH₃) was isolated as [Nb(μ-OEt)-(ONp)₄]₂ (1, Np = CH₂C(CH₃)₃) by alcoholysis exchange. 1 crystallized in an edge-shared bioctahedral dinuclear arrangement with the smaller ligands acting as the bridging moieties. Multidentate ligands such as bis(hydroxymethyl)propionic acid (BHMP-H₃) and tris-(hydroxymethyl)ethane (THME-H₃) were independently reacted with Nb(OEt)₅ to reduce the number of terminal ligands, yielding [(μ-BHMP)Nb₂(μ-O)(OEt)₅]₂ (2) and [(μ-THME)-Nb(OEt)₂]₂ (3) respectively. For 2, two unsymmetrical "(EtO)₂Nb(μ-O)Nb(OEt)₃" units are bridged by two tetradentate BHMP ligands. The THME moiety of 3 acts as a chelating, unidentate-bridging ligand forming a symmetrical dinuclear species, wherein each Nb atom possesses two terminal ethoxides. The synthesis, characterization, structural aspects, and solution properties of 1-3 are reported. The resulting morphological and electrical changes in the properties of the resulting electroceramic PMN and PNZT films due to the incorporation of these Nb alkoxides are also reported.

Original language	English (US)
Pages (from-to)	3187-3198
Number of pages	12
Journal	Chemistry of Materials
Volume	9
Issue number	12
DOIs	https://doi.org/10.1021/cm970506p
State	Published - Dec 1997
Externally published	Yes

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

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Boyle, T. J., Alam, T. M., Dimos, D., Moore, G. J., Buchheit, C. D., Al-Shareef, H. N., Mechenbier, E. R., Bear, B. R., & Ziller, J. W. (1997). Niobium(V) Alkoxides. Synthesis, Structure, and Characterization of [Nb(μ-OCH₂CH₃)(OCH₂C(CH₃) ₃)₄]₂, {[H₃CC(CH₂O)(CH₂-μ-O)(C(O) ₂)]Nb₂(μ-O)(OCH₂CH₃) ₅}₂. Chemistry of Materials, 9(12), 3187-3198. https://doi.org/10.1021/cm970506p

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title = "Niobium(V) Alkoxides. Synthesis, Structure, and Characterization of [Nb(μ-OCH2CH3)(OCH2C(CH3) 3)4]2, {[H3CC(CH2O)(CH2-μ-O)(C(O) 2)]Nb2(μ-O)(OCH2CH3) 5}2",

abstract = "We have synthesized and isolated a number of unique niobium alkoxide compounds and introduced them into novel solution processes for the production of lead magnesium niobate oxide (PMN) and niobium-doped lead zirconate titanate oxide (PNZT) materials. A more sterically demanding analogue to Nb(OEt)5 (Et = CH2CH3) was isolated as [Nb(μ-OEt)-(ONp)4]2 (1, Np = CH2C(CH3)3) by alcoholysis exchange. 1 crystallized in an edge-shared bioctahedral dinuclear arrangement with the smaller ligands acting as the bridging moieties. Multidentate ligands such as bis(hydroxymethyl)propionic acid (BHMP-H3) and tris-(hydroxymethyl)ethane (THME-H3) were independently reacted with Nb(OEt)5 to reduce the number of terminal ligands, yielding [(μ-BHMP)Nb2(μ-O)(OEt)5]2 (2) and [(μ-THME)-Nb(OEt)2]2 (3) respectively. For 2, two unsymmetrical {"}(EtO)2Nb(μ-O)Nb(OEt)3{"} units are bridged by two tetradentate BHMP ligands. The THME moiety of 3 acts as a chelating, unidentate-bridging ligand forming a symmetrical dinuclear species, wherein each Nb atom possesses two terminal ethoxides. The synthesis, characterization, structural aspects, and solution properties of 1-3 are reported. The resulting morphological and electrical changes in the properties of the resulting electroceramic PMN and PNZT films due to the incorporation of these Nb alkoxides are also reported.",

author = "Boyle, {Timothy J.} and Alam, {Todd M.} and Duane Dimos and Moore, {Gregorio J.} and Buchheit, {Catherine D.} and Al-Shareef, {Husam N.} and Mechenbier, {Eric R.} and Bear, {Blakely R.} and Ziller, {Joseph W.}",

year = "1997",

month = dec,

doi = "10.1021/cm970506p",

language = "English (US)",

volume = "9",

pages = "3187--3198",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "AMER CHEMICAL SOC",

number = "12",

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T1 - Niobium(V) Alkoxides. Synthesis, Structure, and Characterization of [Nb(μ-OCH2CH3)(OCH2C(CH3) 3)4]2, {[H3CC(CH2O)(CH2-μ-O)(C(O) 2)]Nb2(μ-O)(OCH2CH3) 5}2

AU - Boyle, Timothy J.

AU - Alam, Todd M.

AU - Dimos, Duane

AU - Moore, Gregorio J.

AU - Buchheit, Catherine D.

AU - Al-Shareef, Husam N.

AU - Mechenbier, Eric R.

AU - Bear, Blakely R.

AU - Ziller, Joseph W.

PY - 1997/12

Y1 - 1997/12

N2 - We have synthesized and isolated a number of unique niobium alkoxide compounds and introduced them into novel solution processes for the production of lead magnesium niobate oxide (PMN) and niobium-doped lead zirconate titanate oxide (PNZT) materials. A more sterically demanding analogue to Nb(OEt)5 (Et = CH2CH3) was isolated as [Nb(μ-OEt)-(ONp)4]2 (1, Np = CH2C(CH3)3) by alcoholysis exchange. 1 crystallized in an edge-shared bioctahedral dinuclear arrangement with the smaller ligands acting as the bridging moieties. Multidentate ligands such as bis(hydroxymethyl)propionic acid (BHMP-H3) and tris-(hydroxymethyl)ethane (THME-H3) were independently reacted with Nb(OEt)5 to reduce the number of terminal ligands, yielding [(μ-BHMP)Nb2(μ-O)(OEt)5]2 (2) and [(μ-THME)-Nb(OEt)2]2 (3) respectively. For 2, two unsymmetrical "(EtO)2Nb(μ-O)Nb(OEt)3" units are bridged by two tetradentate BHMP ligands. The THME moiety of 3 acts as a chelating, unidentate-bridging ligand forming a symmetrical dinuclear species, wherein each Nb atom possesses two terminal ethoxides. The synthesis, characterization, structural aspects, and solution properties of 1-3 are reported. The resulting morphological and electrical changes in the properties of the resulting electroceramic PMN and PNZT films due to the incorporation of these Nb alkoxides are also reported.

AB - We have synthesized and isolated a number of unique niobium alkoxide compounds and introduced them into novel solution processes for the production of lead magnesium niobate oxide (PMN) and niobium-doped lead zirconate titanate oxide (PNZT) materials. A more sterically demanding analogue to Nb(OEt)5 (Et = CH2CH3) was isolated as [Nb(μ-OEt)-(ONp)4]2 (1, Np = CH2C(CH3)3) by alcoholysis exchange. 1 crystallized in an edge-shared bioctahedral dinuclear arrangement with the smaller ligands acting as the bridging moieties. Multidentate ligands such as bis(hydroxymethyl)propionic acid (BHMP-H3) and tris-(hydroxymethyl)ethane (THME-H3) were independently reacted with Nb(OEt)5 to reduce the number of terminal ligands, yielding [(μ-BHMP)Nb2(μ-O)(OEt)5]2 (2) and [(μ-THME)-Nb(OEt)2]2 (3) respectively. For 2, two unsymmetrical "(EtO)2Nb(μ-O)Nb(OEt)3" units are bridged by two tetradentate BHMP ligands. The THME moiety of 3 acts as a chelating, unidentate-bridging ligand forming a symmetrical dinuclear species, wherein each Nb atom possesses two terminal ethoxides. The synthesis, characterization, structural aspects, and solution properties of 1-3 are reported. The resulting morphological and electrical changes in the properties of the resulting electroceramic PMN and PNZT films due to the incorporation of these Nb alkoxides are also reported.

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U2 - 10.1021/cm970506p

DO - 10.1021/cm970506p

M3 - Article

AN - SCOPUS:0000596782

SN - 0897-4756

VL - 9

SP - 3187

EP - 3198

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 12

ER -

Niobium(V) Alkoxides. Synthesis, Structure, and Characterization of [Nb(μ-OCH₂CH₃)(OCH₂C(CH₃) ₃)₄]₂, {[H₃CC(CH₂O)(CH₂-μ-O)(C(O) ₂)]Nb₂(μ-O)(OCH₂CH₃) ₅}₂

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