skip to main content
OSTI.GOV 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

Journal Article · · Inorganic Chemistry
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)
+ Show Author Affiliations

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.

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1473938
Report Number(s):
SAND-2018-10056J; 667861
Journal Information:
Inorganic Chemistry, Vol. 57, Issue 15; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

References (48)

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
Novel mononuclear zirconium and hafnium alkoxides; improved precursors for the MOCVD of ZrO2 and HfO2 journal December 2001
Investigation of Eu$^{2+}$ Doped Barium Silicates as Scintillators journal April 2012
A comparison of BGO and BSO crystals used in the dual-readout mode
  • 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 https://doi.org/10.1016/j.nima.2011.03.013
journal June 2011
The first examples of X-ray phosphors, and C-band infrared emitters based on microporous lanthanide silicates journal July 2004
Ce3+ doped inorganic scintillators
  • 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 https://doi.org/10.1016/0168-9002(94)90798-6
journal September 1994
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
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
Recent progress in the development of Li2MnSiO4 cathode materials journal May 2014
Photocatalytical Nanocomposites: A Review journal February 2014
Reactivity and applications of layered silicates and layered double hydroxides journal January 2014
Atomic layer deposition of hafnium silicate film for high mobility pentacene thin film transistor applications journal January 2009
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
From Molecular Gallium and Indium Siloxide Precursors to Amorphous Semiconducting Transparent Oxide Layers for Applications in Thin-Film Field-Effect Transistors journal July 2012
Structural Relationships in High-Nuclearity Heterobimetallic Bismuth-Oxo Clusters journal December 2005
Atomic layer deposition of hafnium silicate films using hafnium tetrachloride and tetra-n-butyl orthosilicate journal July 2004
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
Trisilane-1,3-diolato Complexes of Ti and Zr:  Syntheses and X-ray Crystal Structures journal March 2006
General Route to Homogeneous, Mesoporous, Multicomponent Oxides Based on the Thermolytic Transformation of Molecular Precursors in Non-polar Media journal March 2001
Block Copolymer-Assisted Synthesis of Mesoporous, Multicomponent Oxides by Nonhydrolytic, Thermolytic Decomposition of Molecular Precursors in Nonpolar Media journal October 2001
A Molecular Precursor Route to Active and Selective Vanadia−Silica−Zirconia Heterogeneous Catalysts for the Oxidative Dehydrogenation of Propane journal September 1998
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
Trialkoxysiloxy complexes as precursors to MO2.cntdot.4SiO2 (M = Ti, Zr, Hf) materials journal November 1991
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
Ferrous tris(trimethylsilyl) silanolates: synthesis, structure, reactivity and thermal decomposition journal November 1997
Synthesis of Tantalum(V) Amido Silyl Complexes and the Unexpected Formation of (Me 2 N) 3 Ta( η 2 -ONMe 2 )[OSi(SiMe 3 ) 3 ] from the Reaction of (Me 2 N) 4 Ta[Si(SiMe 3 ) 3 ] with O 2 journal September 2002
Highly branched-chain methylhalo polysilanes journal February 1966
Lithium and sodiumtris(trimethylsilyl)silanolates. Synthesis and reactivity journal June 1995
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 3 (μ 3 -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
Series of Comparable Dinuclear Group 4 Neo-pentoxide Precursors for Production of pH Dependent Group 4 Nanoceramic Morphologies journal December 2010
Crystal structure refinement with SHELXL journal January 2015
A short history of SHELX journal December 2007
OLEX2 : a complete structure solution, refinement and analysis program journal January 2009
Infrared and Raman Spectroscopic Studies of Tris(trimethylsilyl)silane Derivatives of ((CH3)3Si)3Si-X [X = H, Cl, OH, CH3, OCH3, Si(CH3)3]: Vibrational Assignments by Hartree-Fock and Density-functional Theory Calculations journal November 2011
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
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

Cited By (2)

Lead(II) Siloxides journal November 2019
Barium Siloxides and Catalysed Formation of Si−O−Si' Motifs journal August 2019

Linked Research (18)

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY