DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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 (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))66-0)] (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 generatingmore » 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.« 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:
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. https://doi.org/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. https://doi.org/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},
number = 15,
volume = 57,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Improved scintillation time response in (Lu 0.5 Gd 0.5 ) 2 O 3  : Eu 3+ compared with Lu 2 O 3  : Eu 3+ transparent ceramics
journal, May 2011


Defect states in Pr3+ doped lutetium pyrosilicate
journal, March 2012


Doped Lutetium Silicates Scintillators Prepared by Sol-Gel Method. The Effect of Stoichiometry on Phase Relations and Luminescent Properties
journal, March 2011

  • Niznansky, D.; Begnamini, A.; Vejpravova-Poltierova, J.
  • IOP Conference Series: Materials Science and Engineering, Vol. 18, Issue 10
  • DOI: 10.1088/1757-899X/18/10/102020

Novel mononuclear zirconium and hafnium alkoxides; improved precursors for the MOCVD of ZrO2 and HfO2
journal, December 2001

  • Williams, Paul A.; Roberts, John L.; Jones, Anthony C.
  • Journal of Materials Chemistry, Vol. 12, Issue 2
  • DOI: 10.1039/b109994a

Investigation of Eu$^{2+}$ Doped Barium Silicates as Scintillators
journal, April 2012

  • Eagleman, Yetta; Bourret-Courchesne, Edith; Derenzo, Stephen E.
  • IEEE Transactions on Nuclear Science, Vol. 59, Issue 2
  • DOI: 10.1109/TNS.2011.2179559

A comparison of BGO and BSO crystals used in the dual-readout mode
journal, June 2011

  • Akchurin, N.; Bedeschi, F.; Cardini, A.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 640, Issue 1
  • DOI: 10.1016/j.nima.2011.03.013

The first examples of X-ray phosphors, and C-band infrared emitters based on microporous lanthanide silicates
journal, July 2004


Ce3+ doped inorganic scintillators
journal, September 1994

  • van Eijk, C. W. E.; Andriessen, J.; Dorenbos, P.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 348, Issue 2-3
  • DOI: 10.1016/0168-9002(94)90798-6

High Efficiency of Lutetium Silicate Scintillators, Ce-Doped LPS and LYSO Crystals for Medical Applications
journal, September 2007


Luminescence properties of Tb 3+ -activated silicate glass scintillator
journal, January 2011

  • Sun, Xin-yuan; Zhang, Min; Yu, Xiao-guang
  • International Journal of Materials Research, Vol. 102, Issue 1
  • DOI: 10.3139/146.110452

Poly(methacrylic acid)-graft-Ni3Si2O5(OH)4 multiwalled nanotubes as a novel nanosorbent for effective removal of copper(II) ions
journal, August 2016


Optical, FTIR and DC Conductivity of Soda Lime Silicate Glass Containing Cement Dust and Transition Metal Ions
journal, December 2015


Highly Efficient pc-LED Phosphors Sr 1-x Ba x Si 2 O 2 N 2 :Eu 2+ (0 x 1) - Crystal Structures and Luminescence Properties Revisited
journal, March 2014

  • Seibald, Markus; Rosenthal, Tobias; Oeckler, Oliver
  • Critical Reviews in Solid State and Materials Sciences, Vol. 39, Issue 3
  • DOI: 10.1080/10408436.2013.863175

Recent progress in the development of Li2MnSiO4 cathode materials
journal, May 2014


Photocatalytical Nanocomposites: A Review
journal, February 2014

  • Matějka, Vlastimil; Tokarský, Jonáš
  • Journal of Nanoscience and Nanotechnology, Vol. 14, Issue 2
  • DOI: 10.1166/jnn.2014.9081

Reactivity and applications of layered silicates and layered double hydroxides
journal, January 2014

  • Selvam, Thangaraj; Inayat, Alexandra; Schwieger, Wilhelm
  • Dalton Transactions, Vol. 43, Issue 27
  • DOI: 10.1039/c4dt00573b

Atomic layer deposition of hafnium silicate film for high mobility pentacene thin film transistor applications
journal, January 2009

  • Lee, Seunghyup; Yun, Dong-Jin; Rhee, Shi-Woo
  • Journal of Materials Chemistry, Vol. 19, Issue 37
  • DOI: 10.1039/b908216f

Preparation of alkaline-earth metal silicates from gels and their NOx-adsorption behavior
journal, January 2004


Amine catalyzed condensation of tetraethylorthosilicate
journal, October 2001


Fluorescence and Fluorescence-Excitation Spectra of Benzo[ f ]quinoline during the Sol–Gel–Xerogel Transitions of Mixed Silicon–Aluminum Alkoxide Systems
journal, August 1993

  • Mabuchi, Toshiaki; Fujii, Tsuneo
  • Bulletin of the Chemical Society of Japan, Vol. 66, Issue 8
  • DOI: 10.1246/bcsj.66.2174

Structural Relationships in High-Nuclearity Heterobimetallic Bismuth-Oxo Clusters
journal, December 2005

  • Mehring, Michael; Paalasmaa, Sanna; Schürmann, Markus
  • European Journal of Inorganic Chemistry, Vol. 2005, Issue 24
  • DOI: 10.1002/ejic.200500636

Atomic layer deposition of hafnium silicate films using hafnium tetrachloride and tetra-n-butyl orthosilicate
journal, July 2004

  • Kim, Won-Kyu; Rhee, Shi-Woo; Lee, Nae-In
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 22, Issue 4
  • DOI: 10.1116/1.1764819

Diastereoselective formation of a meso-disilane-1,2-diol – a dianionic siloxide ligand for Ti and Zr
journal, October 2004


Synthesis and Structures of Titanium and Zirconium Trisiloxides
journal, December 2008

  • Krempner, Clemens; Jäger-Fiedler, Ulrike; Köckerling, Martin
  • Organometallics, Vol. 28, Issue 1
  • DOI: 10.1021/om800930s

Trisilane-1,3-diolato Complexes of Ti and Zr:  Syntheses and X-ray Crystal Structures
journal, March 2006

  • Krempner, C.; Köckerling, M.; Reinke, H.
  • Inorganic Chemistry, Vol. 45, Issue 8
  • DOI: 10.1021/ic0514997

Block Copolymer-Assisted Synthesis of Mesoporous, Multicomponent Oxides by Nonhydrolytic, Thermolytic Decomposition of Molecular Precursors in Nonpolar Media
journal, October 2001

  • Kriesel, Joshua W.; Sander, Melissa S.; Tilley, T. Don
  • Chemistry of Materials, Vol. 13, Issue 10
  • DOI: 10.1021/cm010068t

A Molecular Precursor Route to Active and Selective Vanadia−Silica−Zirconia Heterogeneous Catalysts for the Oxidative Dehydrogenation of Propane
journal, September 1998

  • Rulkens, Ron; Tilley, T. Don
  • Journal of the American Chemical Society, Vol. 120, Issue 38
  • DOI: 10.1021/ja981798d

Tris( tert- butoxy)siloxy Complexes as Single-Source Precursors to Homogeneous Zirconia- and Hafnia-Silica Materials. An Alternative to the Sol-Gel Method
journal, October 1997

  • Terry, Karl W.; Lugmair, Claus G.; Tilley, T. Don
  • Journal of the American Chemical Society, Vol. 119, Issue 41
  • DOI: 10.1021/ja971405v

Trialkoxysiloxy complexes as precursors to MO2.cntdot.4SiO2 (M = Ti, Zr, Hf) materials
journal, November 1991

  • Terry, Karl W.; Tilley, T. Don
  • Chemistry of Materials, Vol. 3, Issue 6
  • DOI: 10.1021/cm00018a008

The tris(trimethylsilyl)silyl group in organic, coordination and organometallic chemistry
journal, November 2004


Cobalt(II) and iron(II) tris(trimethylsilyl)siloxides: synthesis, structure and reactivity
journal, January 2002

  • Chesnokova, Tatiana A.; Zhezlova, Elena V.; Kornev, Alexander N.
  • Journal of Organometallic Chemistry, Vol. 642, Issue 1-2
  • DOI: 10.1016/S0022-328X(01)01095-6

Ferrous tris(trimethylsilyl) silanolates: synthesis, structure, reactivity and thermal decomposition
journal, November 1997


Highly branched-chain methylhalo polysilanes
journal, February 1966


Lithium and sodiumtris(trimethylsilyl)silanolates. Synthesis and reactivity
journal, June 1995

  • Kornev, A. N.; Chesnokova, T. A.; Semenov, V. V.
  • Russian Chemical Bulletin, Vol. 44, Issue 6
  • DOI: 10.1007/BF00707063

Spectroscopic and AM1 semiempirical studies of vibrations of tris(trimethylsilyl)silane derivatives, (Me3Si)3SiX (X  H, Cl, OH, OD, Me, OMe, SiMe3)
journal, September 1992


Titanium(IV) Neopentoxides. X-ray Structures of Ti 33 -O)(μ 3 -Cl)(μ-OCH 2 CMe 3 ) 3 (OCH 2 CMe 3 ) 6 and [Ti(μ-OCH 2 CMe 3 )(OCH 2 CMe 3 ) 3 ] 2
journal, July 1997

  • Boyle, Timothy J.; Alam, Todd M.; Mechenbier, Eric R.
  • Inorganic Chemistry, Vol. 36, Issue 15
  • DOI: 10.1021/ic960924g

Series of Comparable Dinuclear Group 4 Neo-pentoxide Precursors for Production of pH Dependent Group 4 Nanoceramic Morphologies
journal, December 2010

  • Boyle, Timothy J.; Ottley, Leigh Anna M.; Hoppe, Sarah M.
  • Inorganic Chemistry, Vol. 49, Issue 23
  • DOI: 10.1021/ic101205d

Crystal structure refinement with SHELXL
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009

  • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
  • Journal of Applied Crystallography, Vol. 42, Issue 2
  • DOI: 10.1107/S0021889808042726

Infrared spectra-structure correlations for organosilicon compounds
journal, January 1960


Spectra and structure of silicon compounds. XVII Raman and infrared spectra and vibrational assignment for hexamethyldisilane and ab initio calculations for disilane and hexamethyldisilane
journal, March 1994

  • Church, J. S.; Durig, J. R.; Mohamed, Tarek A.
  • Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 50, Issue 3
  • DOI: 10.1016/0584-8539(94)80175-4

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


Core/Shell Nanoparticles: Classes, Properties, Synthesis Mechanisms, Characterization, and Applications
journal, December 2011

  • Ghosh Chaudhuri, Rajib; Paria, Santanu
  • Chemical Reviews, Vol. 112, Issue 4
  • DOI: 10.1021/cr100449n

Works referencing / citing this record:

Lead(II) Siloxides
journal, November 2019

  • Someşan, Adrian‐Alexandru; Le Coz, Erwann; Raţ, Ciprian Ionuţ
  • Chemistry – A European Journal, Vol. 25, Issue 71
  • DOI: 10.1002/chem.201904713

Barium Siloxides and Catalysed Formation of Si−O−Si' Motifs
journal, August 2019

  • Le Coz, Erwann; Kahlal, Samia; Saillard, Jean‐Yves
  • Chemistry – A European Journal, Vol. 25, Issue 59
  • DOI: 10.1002/chem.201903676