Titanium(IV) Neopentoxides. X-ray Structures of Ti3(μ3-O)(μ3-Cl)-(μ-OCH2CMe3)3(OCH2CMe3)6 and [Ti(μ-OCH2CMe3)-(OCH2CMe3)3]2

Boyle, Timothy J.; Alam, Todd M.; Mechenbier, Eric R.; Scott, Brian L.

doi:10.1021/ic971335t

Cited by 6 publications

(10 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore, determining the coordination behavior of the SST ligand for early transition [M(OR) n ] species was warranted. The group 4 and 5 [M(OR) x ] species were selected for the initial investigation using the commercially available OEt, OPr i , or OBu, as well as the synthesized ONep , alkoxy compounds. The (i) synthesis, (ii) characterization, (iii) materials production, and (iv) nanomaterial properties are discussed below.…”

Section: Resultsmentioning

confidence: 99%

“…The following chemicals were used as received (Aldrich and Alfa Aesar): tris(trimethylsilyl)silane (H–Si(Si(CH 3 ) 3 ) 3 ), triethylamine (N(Et) 3 ), sodium sulfate (Na 2 SO 4 ), neo -pentanol (H-ONep), titanium iso -propoxide ([Ti(OPr i ) 4 ]), titanium n -butoxide ([Ti(OBu n ) 4 ]), metal tert -butoxides [M(OBu t ) 4 ] (M = Ti, Zr, Hf)], vanadium oxo iso -propoxide ([V(O)(OPr i ) 3 ]), vanadium oxo chloride ([V(O)(Cl) 3 ]), niobium ethoxide ([Nb(OEt) 5 ], and tantalum ethoxide ([Ta(OEt) 5 ]). The metal ONep derivatives {[Ti(μ-ONep)(ONep) 3 ] 2 (referred to as [Ti(ONep) 4 ]) and [M 2 (ONep) 8 (OBu t )] 2 (M = Zr, Hf; referred to as [Zr(ONep) 4 ], [Hf(ONep) 4 ], respectively)} were synthesized according to literature procedures. In-house deionized (DI) water (Millipore) was used without further purification.…”

Section: Experimental Sectionmentioning

confidence: 99%

See 1 more Smart Citation

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

et al. 2018

Self Cite

View full text Add to dashboard Cite

In an effort to generate single-source precursors for the production of metal-siloxide (MSiO ) materials, the tris(trimethylsilyl)silanol (H-SST or H-OSi(SiMe) (1) ligand was reacted with a series of group 4 and 5 metal alkoxides. The group 4 products were crystallographically characterized as [Ti(SST)(OR)] (OR = OPr (2), OBu (3), ONep (4)); [Ti(SST)(OBu )] (5); [Zr(SST)(OBu )(py)] (6); [Zr(SST)(OR)] (OR = OBu (7), ONep, (8)); [Hf(SST)(OBu )] (9); and [Hf(SST)(ONep)(py) ] ( n = 1 (10), n = 2 (10a)) where OPr = OCH(CH), OBu = OC(CH), OBu = O(CH)CH, ONep = OCHC(CH), py = pyridine. The crystal structures revealed varied SST substitutions for: 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)(py)] (11), [Nb(SST)(OEt)] (12), [Nb(O)(SST)(py)] (13), 2[H][(Nb(μ-O)(SST))(μ-O)] (14), [NbO(OEt)(SST)·1/5NaO] (15), [Ta(SST)(μ-OEt)(OEt)] (16), and [Ta(SST)(OEt)] (17) where OEt = OCHCH. 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 materials. The complexes were thermally processed (350-1100 °C, 4 h, ambient atmosphere), but instead of the desired MSiO, transmission electron microscopy analyses revealed that fractions of the group 4 and group 5 precursors had formed unusual metal oxide silica architectures.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Experimental Sectionmentioning

confidence: 99%

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

et al. 2018

Self Cite

View full text Add to dashboard Cite

show abstract

“…Titanium neopentoxide ([Ti(ONep) 4 ]) was synthesized from the reaction of [Ti(OPr i ) 4 ] with H-ONep according to the literature routes. 25 FTIR data were collected on a Nicolet 6700 FTIR spectrometer using a KBr pellet press under a flowing atmosphere of nitrogen or with an iD7 ATR accessory mounted with a monolithic diamond crystal. Elemental analyses were collected on a PerkinElmer 2400 Series II CHNS/O Analyzer with samples prepared in an argon-filled glovebox.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides

et al. 2019

Self Cite

View full text Add to dashboard Cite

A series of titanium alkoxides ([Ti(OR) 4 ] (OR = OCH(CH 3 ) 2 (OPr i ), OC(CH 3 ) 3 (OBu t ), and OCH 2 C(CH 3 ) 3 (ONep)) were modified with a set of substituted hydroxyl-benzaldehydes [HO-BzA-L x : x = 1, 2-hydroxybenzaldehyde (L = H), 2-hydroxy-3-methoxybenzaldehyde (OMe-3), 5-bromo-2-hydroxybenzaldehyde (Br-5), 2-hydroxy-5-nitrobenzaldehyde (NO 2 -5); x = 2, 3,5-di-tert-butyl-2-hydroxybenzaldehyde (Bu t -3,5), 2-hydroxy-3,5-diiodobenzaldehyde (I-3,5)] in pyridine (py). Instead of the expected simple substitution, each of the HO-BzA-L x modifiers were reduced to their respective diol [(py , NO 2 -5 (4a•4py); x = 2, Bu t -3,5 (5a), I-3,5 (6a), ONep; x = 1, L = H (1b), OMe-3 (2b), Br-5 (3b•py), NO 2 -5 (4b); x = 2, Bu t -3,5 (5b), I-3,5 (6b•py)), as identified by single crystal X-ray studies. The 1 H NMR spectral data were complex at room temperature but simplified at high temperatures (70 °C). Diffusion ordered spectroscopy (DOSY) NMR experiments indicated that 2a maintained the dinuclear structure in a solution independent of the temperature, whereas 2b appears to be monomeric over the same temperature range. On the basis of additional NMR studies, the mechanism of the reduction of the HO-BzA-L x to the dioxide ligand was thought to occur by a Meerwein−Pondorf−Verley (MPV) mechanism. The structures of 1a−6b appear to be the intermediate dioxide products of the MPV reduction, which became "trapped" by the Lewis basic solvate.

show abstract

“…The parent alkoxides [M(ONep) 4 ] 2 (M = Ti, Zr, and Hf) and the complementary AM-DBP 2 /ONep ligated compounds 2 , 5 , and 7 were used to generate nanomaterials under solvothermal (SOLVO; octadecene) conditions. A comparison of the final materials was undertaken using dynamic light scattering (DLS), transmission electron microscopy (TEM), and powder X-ray diffraction (PXRD) to determine the influence that the AM-DBP 2 ligand has on the thermal properties of the precursor and final materials’ properties.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Nanomaterials Generated from 6,6′-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) Modified Group 4 Metal Alkoxides

et al. 2018

Self Cite

View full text Add to dashboard Cite

The impact on the morphology nanoceramic materials generated from group 4 metal alkoxides ([M(OR)]) and the same precursors modified by 6,6'-(((2-hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di- tert-butylphenol) (referred to as H-AM-DBP (1)) was explored. The products isolated from the 1:1 stoichiometric reaction of a series of [M(OR)] where M = Ti, Zr, or Hf; OR = OCH(CH)(OPr ); OC(CH)(OBu ); OCHC(CH)(ONep) with H-AM-DBP proved, by single crystal X-ray diffraction, to be [(ONep)Ti( k( O,O',O'',N)-AM-DBP)] (2), [(OR)M(μ( O)- k( O',O'',N)-AM-DBP)] [M = Zr: OR = OPr , 3·tol; OBu, 4·tol; ONep, 5·tol; M = Hf: OR = OBu , 6·tol; ONep, 7·tol]. The product from each system led to a tetradentate AM-DBP ligand and retention of a parent alkoxide ligand. For the monomeric Ti derivative (2), the metal was solved in a trigonal bipyramidal geometry, whereas for the Zr (3-5) and Hf (6, 7) derivatives a symmetric dinuclear complex was formed where the ethoxide moiety of the AM-DBP ligand bridges to the other metal center, generating an octahedral geometry. High quality density functional theory level gas-phase electronic structure calculations on compounds 2-7 using Gaussian 09 were used for meaningful time dependent density functional theory calculations in the interpretation of the UV-vis absorbance spectral data on 2-7. Nanoparticles generated from the solvothermal treatment of the ONep/AM-DBP modified compounds (2, 5, 7) in comparison to their parent [M(ONep)] were larger and had improved regularity and dispersion of the final ceramic nanomaterials.

show abstract

Titanium(IV) Neopentoxides. X-ray Structures of Ti₃(μ₃-O)(μ₃-Cl)-(μ-OCH₂CMe₃)₃(OCH₂CMe₃)₆ and [Ti(μ-OCH₂CMe₃)-(OCH₂CMe₃)₃]₂

Cited by 6 publications

References 0 publications

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

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

Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides

Synthesis, Characterization, and Nanomaterials Generated from 6,6′-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) Modified Group 4 Metal Alkoxides

Contact Info

Product

Resources

About