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Title: Synthesis and Characterization of Tris(trimethylsilyl)siloxide Derivatives of Early Transition Metal Alkoxides That Thermally Convert to Varied Ceramic–Silica Architecture Materials

Abstract

In an effort to generate single-source precursors for the production of metal-siloxide (MSiO x) materials, the tris(trimethylsilyl)silanol (H-SST or H-OSi(SiMe 3) 3 (1) ligand was reacted with a series of group 4 and 5 metal alkoxides. The group 4 products were crystallographically characterized as: [Ti(SST) 2(OR) 2] (OR = OPr i (2), OBu t (3), ONep (4)); [Ti(SST) 3(OBu n)] (5); [Zr(SST) 2(OBu t) 2(py)] (6); [Zr(SST) 3(OR)] (OR = OBu t(7), ONep, (8)); [Hf(SST) 2(OBu t) 2] (9); and [Hf(SST) 2(ONep) 2(py) n] (n = 1 (10) , n = 2 (10a)) where OPr i = OCH(CH 3) 2, OBu t = OC(CH 3) 3, OBu n = O(CH 2) 3CH 3, ONep = OCH 2C(CH 3) 3, py = pyridine. The crystal structures revealed SST substituted: monomeric Ti species that adopted a tetrahedral (T-4) geometry; monomeric Zr compounds with coordination that varied from T-4 to trigonal bipyramidal (TBPY- 5); and monomeric Hf complexes isolated in a TBPY-5 geometry. For the group 5 species, the following derivatives were structurally identified as: [V(SST) 3(py) 2] (11), [Nb(SST) 3(OEt) 2] (12), [Nb(0)(SST) 3(py)] (13), 2[H][(Nb(μ-0) 2(SST)) 66-0)] (14), [Nb 8O 10(OEt) 18(SST) 2•1/5Na 2O] (15), [Ta(SST)([μ-OEt)(OEt) 3] 2(16), and [Ta(SST)more » 3(OEt) 2] (17) where OEt = OCH 2CH 3. The group 5 monomeric complexes were solved in a TBPY-5 arrangement, whereas the Ta of the dinculear 16 was solved in an octahedral coordination environment. Thermal analyses of these precursors revealed a stepwise loss of ligand, which indicated their potential utility for generating the MSiO x, materials. The complexes were thermally processed (350 - 1100 °C, 4h, ambient atmosphere) but instead of the desired MSiO x, transmission electron microscopy analyses revealed fractions of the group 4 and group 5 precursors had formed unusual architectures.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [1];  [1];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Univ. of Hawaii, Manoa, HI (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1473938
Report Number(s):
SAND-2018-10056J
Journal ID: ISSN 0020-1669; 667861
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 15; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Boyle, Timothy J., Sears, Jeremiah M., Perales, Diana, Cramer, Roger E., Lu, Ping, Chan, Rana O., and Hernandez-Sanchez, Bernadette A. Synthesis and Characterization of Tris(trimethylsilyl)siloxide Derivatives of Early Transition Metal Alkoxides That Thermally Convert to Varied Ceramic–Silica Architecture Materials. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b00630.
Boyle, Timothy J., Sears, Jeremiah M., Perales, Diana, Cramer, Roger E., Lu, Ping, Chan, Rana O., & Hernandez-Sanchez, Bernadette A. Synthesis and Characterization of Tris(trimethylsilyl)siloxide Derivatives of Early Transition Metal Alkoxides That Thermally Convert to Varied Ceramic–Silica Architecture Materials. United States. doi:10.1021/acs.inorgchem.8b00630.
Boyle, Timothy J., Sears, Jeremiah M., Perales, Diana, Cramer, Roger E., Lu, Ping, Chan, Rana O., and Hernandez-Sanchez, Bernadette A. Fri . "Synthesis and Characterization of Tris(trimethylsilyl)siloxide Derivatives of Early Transition Metal Alkoxides That Thermally Convert to Varied Ceramic–Silica Architecture Materials". United States. doi:10.1021/acs.inorgchem.8b00630. https://www.osti.gov/servlets/purl/1473938.
@article{osti_1473938,
title = {Synthesis and Characterization of Tris(trimethylsilyl)siloxide Derivatives of Early Transition Metal Alkoxides That Thermally Convert to Varied Ceramic–Silica Architecture Materials},
author = {Boyle, Timothy J. and Sears, Jeremiah M. and Perales, Diana and Cramer, Roger E. and Lu, Ping and Chan, Rana O. and Hernandez-Sanchez, Bernadette A.},
abstractNote = {In an effort to generate single-source precursors for the production of metal-siloxide (MSiOx) materials, the tris(trimethylsilyl)silanol (H-SST or H-OSi(SiMe3)3 (1) ligand was reacted with a series of group 4 and 5 metal alkoxides. The group 4 products were crystallographically characterized as: [Ti(SST)2(OR)2] (OR = OPri (2), OBut (3), ONep (4)); [Ti(SST)3(OBun)] (5); [Zr(SST)2(OBut)2(py)] (6); [Zr(SST)3(OR)] (OR = OBut(7), ONep, (8)); [Hf(SST)2(OBut)2] (9); and [Hf(SST)2(ONep)2(py)n] (n = 1 (10) , n = 2 (10a)) where OPri = OCH(CH3)2, OBut = OC(CH3)3, OBun = O(CH2)3CH3, ONep = OCH2C(CH3)3, py = pyridine. The crystal structures revealed SST substituted: monomeric Ti species that adopted a tetrahedral (T-4) geometry; monomeric Zr compounds with coordination that varied from T-4 to trigonal bipyramidal (TBPY- 5); and monomeric Hf complexes isolated in a TBPY-5 geometry. For the group 5 species, the following derivatives were structurally identified as: [V(SST)3(py)2] (11), [Nb(SST)3(OEt)2] (12), [Nb(0)(SST)3(py)] (13), 2[H][(Nb(μ-0)2(SST))6(μ6-0)] (14), [Nb8O10(OEt)18(SST)2•1/5Na2O] (15), [Ta(SST)([μ-OEt)(OEt)3]2(16), and [Ta(SST)3(OEt)2] (17) where OEt = OCH2CH3. The group 5 monomeric complexes were solved in a TBPY-5 arrangement, whereas the Ta of the dinculear 16 was solved in an octahedral coordination environment. Thermal analyses of these precursors revealed a stepwise loss of ligand, which indicated their potential utility for generating the MSiOx, materials. The complexes were thermally processed (350 - 1100 °C, 4h, ambient atmosphere) but instead of the desired MSiOx, transmission electron microscopy analyses revealed fractions of the group 4 and group 5 precursors had formed unusual architectures.},
doi = {10.1021/acs.inorgchem.8b00630},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 15,
volume = 57,
place = {United States},
year = {2018},
month = {7}
}

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Works referencing / citing this record:

CCDC 1572784: Experimental Crystal Structure Determination: RIJPAE : triethylammonium chloride tris(tris(trimethylsilyl)silanol)
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CCDC 1572785: Experimental Crystal Structure Determination: RIJPEI : bis(tris(trimethylsilyl)silanolato)-bis(propan-2-olato)-titanium(iv)
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CCDC 1572786: Experimental Crystal Structure Determination: RIJPIM : bis(tris(trimethylsilyl)silanolato)-bis(2-methylpropan-2-olato)-titanium(iv)
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CCDC 1572790: Experimental Crystal Structure Determination: RIJNOQ : (2-methylpropan-2-olato)-tris(tris(trimethylsilyl)silanolato)-zirconium(iv)
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CCDC 1572793: Experimental Crystal Structure Determination: RIJQIN : bis(2-methylpropan-2-olato)-bis(tris(trimethylsilyl)silanolato)-pyridine-hafnium(iv)
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CCDC 1572795: Experimental Crystal Structure Determination: RIJQUZ : tris(tris(trimethylsilyl)silanolato)-bis(pyridine)-vanadium(iii)
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CCDC 1572796: Experimental Crystal Structure Determination: RIJRAG : bis(ethanolato)-tris(tris(trimethylsilyl)silanolato)-niobium(v)
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CCDC 1572797: Experimental Crystal Structure Determination: RIJREK : tris(tris(trimethylsilyl)silanolato)-oxo-pyridine-niobium(v)
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CCDC 1572801: Experimental Crystal Structure Determination: RIJNIK : bis(ethanolato)-tris(tris(trimethylsilyl)silanolato)-tantalum(v)
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