Surface organometallic chemistry of zirconium: Chemical reactivity of the ≡Si-O-ZrNp3 surface complex synthesized on dehydroxylated silica and application to the modification of mordenite

Mariko Adachi; Christophe Nédez; Xu Xu Wang; François Bayard; Véronique Dufaud; Frédéric Lefebvre; Jean Marie Basset

doi:10.1016/S1381-1169(03)00326-1

Surface organometallic chemistry of zirconium: Chemical reactivity of the ≡Si-O-ZrNp₃ surface complex synthesized on dehydroxylated silica and application to the modification of mordenite

Mariko Adachi, Christophe Nédez, Xu Xu Wang, François Bayard, Véronique Dufaud, Frédéric Lefebvre^*, Jean Marie Basset

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

The organometallic complex ≡Si-O-Zr(CH₂C(CH ₃)₃)₃ was synthesized on the surface of silica dehydroxylated at 500 °C and its reactivity towards oxygenated molecules was studied. The materials were characterized by IR, ¹³C CP-MAS NMR, analysis of evolved gases and elemental analysis. Reaction with neopentyl alcohol ((CH₃)₃CCH₂OH) leads to the quantitative formation of ≡Si-O-Zr(OCH₂C(CH₃) ₃)₃. Similarly, reaction with pivalic acid ((CH ₃)₃CCOOH) leads to the quantitative formation of ≡Si-O-Zr(OCOC(CH₃)₃)₃. Addition of dry oxygen at 25 °C to ≡Si-O-Zr(CH₂C(CH₃) ₃)₃ leads to the formation of ≡Si-O-Zr(OCH ₂C(CH₃)₃)₃. When heated at 200 °C under oxygen, the alkoxy ligands transform into carboxylate species ((CH₃)₃CCOO)^- probably coordinated to zirconium. These results, together with molecular modelling studies of the adsorption of hydrocarbons on mordenite modified by such complexes, explain the different behaviours observed in presence of air or inert gases.

Original language	English (US)
Pages (from-to)	443-455
Number of pages	13
Journal	Journal of Molecular Catalysis A: Chemical
Volume	204-205
DOIs	https://doi.org/10.1016/S1381-1169(03)00326-1
State	Published - Sep 15 2003
Externally published	Yes

Keywords

Mordenite
Organometallic
Oxidation
Solid-state NMR
Zirconium

ASJC Scopus subject areas

Catalysis
Process Chemistry and Technology
Physical and Theoretical Chemistry

Access to Document

10.1016/S1381-1169(03)00326-1

Cite this

Adachi, M., Nédez, C., Wang, X. X., Bayard, F., Dufaud, V., Lefebvre, F., & Basset, J. M. (2003). Surface organometallic chemistry of zirconium: Chemical reactivity of the ≡Si-O-ZrNp₃ surface complex synthesized on dehydroxylated silica and application to the modification of mordenite. Journal of Molecular Catalysis A: Chemical, 204-205, 443-455. https://doi.org/10.1016/S1381-1169(03)00326-1

@article{4f68282e0462476cad8b749c4449fbb9,

title = "Surface organometallic chemistry of zirconium: Chemical reactivity of the ≡Si-O-ZrNp3 surface complex synthesized on dehydroxylated silica and application to the modification of mordenite",

abstract = "The organometallic complex ≡Si-O-Zr(CH2C(CH 3)3)3 was synthesized on the surface of silica dehydroxylated at 500 °C and its reactivity towards oxygenated molecules was studied. The materials were characterized by IR, 13C CP-MAS NMR, analysis of evolved gases and elemental analysis. Reaction with neopentyl alcohol ((CH3)3CCH2OH) leads to the quantitative formation of ≡Si-O-Zr(OCH2C(CH3) 3)3. Similarly, reaction with pivalic acid ((CH 3)3CCOOH) leads to the quantitative formation of ≡Si-O-Zr(OCOC(CH3)3)3. Addition of dry oxygen at 25 °C to ≡Si-O-Zr(CH2C(CH3) 3)3 leads to the formation of ≡Si-O-Zr(OCH 2C(CH3)3)3. When heated at 200 °C under oxygen, the alkoxy ligands transform into carboxylate species ((CH3)3CCOO)- probably coordinated to zirconium. These results, together with molecular modelling studies of the adsorption of hydrocarbons on mordenite modified by such complexes, explain the different behaviours observed in presence of air or inert gases.",

keywords = "Mordenite, Organometallic, Oxidation, Solid-state NMR, Zirconium",

author = "Mariko Adachi and Christophe N{\'e}dez and Wang, {Xu Xu} and Fran{\c c}ois Bayard and V{\'e}ronique Dufaud and Fr{\'e}d{\'e}ric Lefebvre and Basset, {Jean Marie}",

year = "2003",

month = sep,

day = "15",

doi = "10.1016/S1381-1169(03)00326-1",

language = "English (US)",

volume = "204-205",

pages = "443--455",

journal = "Journal of Molecular Catalysis A: Chemical",

issn = "1381-1169",

publisher = "Elsevier B.V.",

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Adachi, M, Nédez, C, Wang, XX, Bayard, F, Dufaud, V, Lefebvre, F & Basset, JM 2003, 'Surface organometallic chemistry of zirconium: Chemical reactivity of the ≡Si-O-ZrNp₃ surface complex synthesized on dehydroxylated silica and application to the modification of mordenite', Journal of Molecular Catalysis A: Chemical, vol. 204-205, pp. 443-455. https://doi.org/10.1016/S1381-1169(03)00326-1

Surface organometallic chemistry of zirconium: Chemical reactivity of the ≡Si-O-ZrNp₃ surface complex synthesized on dehydroxylated silica and application to the modification of mordenite. / Adachi, Mariko; Nédez, Christophe; Wang, Xu Xu et al.
In: Journal of Molecular Catalysis A: Chemical, Vol. 204-205, 15.09.2003, p. 443-455.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Surface organometallic chemistry of zirconium

T2 - Chemical reactivity of the ≡Si-O-ZrNp3 surface complex synthesized on dehydroxylated silica and application to the modification of mordenite

AU - Adachi, Mariko

AU - Nédez, Christophe

AU - Wang, Xu Xu

AU - Bayard, François

AU - Dufaud, Véronique

AU - Lefebvre, Frédéric

AU - Basset, Jean Marie

PY - 2003/9/15

Y1 - 2003/9/15

N2 - The organometallic complex ≡Si-O-Zr(CH2C(CH 3)3)3 was synthesized on the surface of silica dehydroxylated at 500 °C and its reactivity towards oxygenated molecules was studied. The materials were characterized by IR, 13C CP-MAS NMR, analysis of evolved gases and elemental analysis. Reaction with neopentyl alcohol ((CH3)3CCH2OH) leads to the quantitative formation of ≡Si-O-Zr(OCH2C(CH3) 3)3. Similarly, reaction with pivalic acid ((CH 3)3CCOOH) leads to the quantitative formation of ≡Si-O-Zr(OCOC(CH3)3)3. Addition of dry oxygen at 25 °C to ≡Si-O-Zr(CH2C(CH3) 3)3 leads to the formation of ≡Si-O-Zr(OCH 2C(CH3)3)3. When heated at 200 °C under oxygen, the alkoxy ligands transform into carboxylate species ((CH3)3CCOO)- probably coordinated to zirconium. These results, together with molecular modelling studies of the adsorption of hydrocarbons on mordenite modified by such complexes, explain the different behaviours observed in presence of air or inert gases.

AB - The organometallic complex ≡Si-O-Zr(CH2C(CH 3)3)3 was synthesized on the surface of silica dehydroxylated at 500 °C and its reactivity towards oxygenated molecules was studied. The materials were characterized by IR, 13C CP-MAS NMR, analysis of evolved gases and elemental analysis. Reaction with neopentyl alcohol ((CH3)3CCH2OH) leads to the quantitative formation of ≡Si-O-Zr(OCH2C(CH3) 3)3. Similarly, reaction with pivalic acid ((CH 3)3CCOOH) leads to the quantitative formation of ≡Si-O-Zr(OCOC(CH3)3)3. Addition of dry oxygen at 25 °C to ≡Si-O-Zr(CH2C(CH3) 3)3 leads to the formation of ≡Si-O-Zr(OCH 2C(CH3)3)3. When heated at 200 °C under oxygen, the alkoxy ligands transform into carboxylate species ((CH3)3CCOO)- probably coordinated to zirconium. These results, together with molecular modelling studies of the adsorption of hydrocarbons on mordenite modified by such complexes, explain the different behaviours observed in presence of air or inert gases.

KW - Mordenite

KW - Organometallic

KW - Oxidation

KW - Solid-state NMR

KW - Zirconium

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U2 - 10.1016/S1381-1169(03)00326-1

DO - 10.1016/S1381-1169(03)00326-1

M3 - Article

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SN - 1381-1169

VL - 204-205

SP - 443

EP - 455

JO - Journal of Molecular Catalysis A: Chemical

JF - Journal of Molecular Catalysis A: Chemical

ER -