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))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 generatingmore »
- Authors:
-
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- 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. 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},
number = 15,
volume = 57,
place = {United States},
year = {2018},
month = {7}
}
Works referencing / citing this record:
CCDC 1572784: Experimental Crystal Structure Determination: RIJPAE : triethylammonium chloride tris(tris(trimethylsilyl)silanol)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572785: Experimental Crystal Structure Determination: RIJPEI : bis(tris(trimethylsilyl)silanolato)-bis(propan-2-olato)-titanium(iv)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572786: Experimental Crystal Structure Determination: RIJPIM : bis(tris(trimethylsilyl)silanolato)-bis(2-methylpropan-2-olato)-titanium(iv)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572787: Experimental Crystal Structure Determination: RIJPOS : bis(tris(trimethylsilyl)silanolato)-bis(2,2-dimethylpropan-1-olato)-titanium(iv)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572788: Experimental Crystal Structure Determination: RIJPUY : (n-butan-1-olato)-tris(tris(trimethylsilyl)silanolato)-titanium(iv)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572789: Experimental Crystal Structure Determination: RIJQAF : bis(2-methylpropan-2-olato)-bis(tris(trimethylsilyl)silanolato)-pyridine-zirconium(iv)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572790: Experimental Crystal Structure Determination: RIJNOQ : (2-methylpropan-2-olato)-tris(tris(trimethylsilyl)silanolato)-zirconium(iv)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572791: Experimental Crystal Structure Determination: RIJNUW : (2,2-dimethylpropan-1-olato)-tris(tris(trimethylsilyl)silanolato)-zirconium(iv)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572792: Experimental Crystal Structure Determination: RIJQEJ : bis(2-methylpropan-2-olato)-bis(tris(trimethylsilyl)silanolato)-hafnium(iv)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572793: Experimental Crystal Structure Determination: RIJQIN : bis(2-methylpropan-2-olato)-bis(tris(trimethylsilyl)silanolato)-pyridine-hafnium(iv)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572794: Experimental Crystal Structure Determination: RIJQOT : bis(2,2-dimethylpropan-1-olato)-bis(tris(trimethylsilyl)silanolato)-bis(pyridine)-hafnium(iv)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572795: Experimental Crystal Structure Determination: RIJQUZ : tris(tris(trimethylsilyl)silanolato)-bis(pyridine)-vanadium(iii)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572796: Experimental Crystal Structure Determination: RIJRAG : bis(ethanolato)-tris(tris(trimethylsilyl)silanolato)-niobium(v)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572797: Experimental Crystal Structure Determination: RIJREK : tris(tris(trimethylsilyl)silanolato)-oxo-pyridine-niobium(v)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572798: Experimental Crystal Structure Determination: RIJRIO : bis(μ-hydroxo)-undecakis(μ-oxido)-hexakis(tris(trimethylsilyl)silanolato)-hexa-niobium(v)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572799: Experimental Crystal Structure Determination: RIJWAL : decakis(μ-oxido)-octakis(μ-ethoxo)-bis(tris(trimethylsilyl)silanolato)-decakis(ethoxo)-octa-niobium sodium toluene solvate hemihydrate
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572800: Experimental Crystal Structure Determination: RIJNEG : bis(μ-ethanolato)-hexakis(ethanolato)-bis(tris(trimethylsilyl)silanolato)-di-tantalum(v)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
CCDC 1572801: Experimental Crystal Structure Determination: RIJNIK : bis(ethanolato)-tris(tris(trimethylsilyl)silanolato)-tantalum(v)
dataset, March 2018
- Boyle, Timothy J.; Sears, Jeremiah M.; Perales, Diana
- Cambridge Structural Database (CSD)
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
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
Lead(II) Siloxides
journal, November 2019
- Someşan, Adrian‐Alexandru; Le Coz, Erwann; Raţ, Ciprian Ionuţ
- Chemistry – A European Journal, Vol. 25, Issue 71