Molecular understanding of the formation of surface zirconium hydrides upon thermal treatment under hydrogen of [(≡SiO)Zr(CH2tBu) 3] by using advanced solid-state NMR techniques

Franck Rataboul; Anne Baudouin; Chloé Thieuleux; Laurent Veyre; Christophe Copéret; Jean Thivolle-Cazat; Jean Marie Basset; Anne Lesage; Lyndon Emsley

doi:10.1021/ja038486h

Molecular understanding of the formation of surface zirconium hydrides upon thermal treatment under hydrogen of [(≡SiO)Zr(CH₂tBu) ₃] by using advanced solid-state NMR techniques

Franck Rataboul, Anne Baudouin, Chloé Thieuleux, Laurent Veyre, Christophe Copéret^*, Jean Thivolle-Cazat, Jean Marie Basset, Anne Lesage, Lyndon Emsley

^*Corresponding author for this work

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

124 Scopus citations

Abstract

The reaction of [(≡SiO)Zr(CH₂tBu)₃] with H ₂ at 150 °C leads to the hydrogenolysis of the zirconium-carbon bonds to form a very reactive hydride intermediate(s), which further reacts with the surrounding siloxane ligands present at the surface of this support to form mainly two different zirconium hydrides: [(≡SiO)₃Zr-H] (1a, 70-80%) and [(≡SiO)₂ZrH₂] (1b, 20-30%) along with silicon hydrides, [(≡SiO)₃SiH] and [(≡SiO) ₂SiH₂]. Their structural identities were identified by ¹H DQ solid-state NMR spectroscopy as well as reactivity studies. These two species react with CO₂ and N₂O to give, respectively, the corresponding formate [(≡SiO)_4-xZr(O-C(=O)H) _x] (2) and hydroxide complexes [(≡SiO)_4-xZr(OH) _x] (x = 1 or 2 for 3a and 3b, respectively) as major surface complexes.

Original language	English (US)
Pages (from-to)	12541-12550
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	126
Issue number	39
DOIs	https://doi.org/10.1021/ja038486h
State	Published - Oct 6 2004
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja038486h

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Rataboul, F., Baudouin, A., Thieuleux, C., Veyre, L., Copéret, C., Thivolle-Cazat, J., Basset, J. M., Lesage, A., & Emsley, L. (2004). Molecular understanding of the formation of surface zirconium hydrides upon thermal treatment under hydrogen of [(≡SiO)Zr(CH₂tBu) ₃] by using advanced solid-state NMR techniques. Journal of the American Chemical Society, 126(39), 12541-12550. https://doi.org/10.1021/ja038486h

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title = "Molecular understanding of the formation of surface zirconium hydrides upon thermal treatment under hydrogen of [(≡SiO)Zr(CH2tBu) 3] by using advanced solid-state NMR techniques",

abstract = "The reaction of [(≡SiO)Zr(CH2tBu)3] with H 2 at 150 °C leads to the hydrogenolysis of the zirconium-carbon bonds to form a very reactive hydride intermediate(s), which further reacts with the surrounding siloxane ligands present at the surface of this support to form mainly two different zirconium hydrides: [(≡SiO)3Zr-H] (1a, 70-80%) and [(≡SiO)2ZrH2] (1b, 20-30%) along with silicon hydrides, [(≡SiO)3SiH] and [(≡SiO) 2SiH2]. Their structural identities were identified by 1H DQ solid-state NMR spectroscopy as well as reactivity studies. These two species react with CO2 and N2O to give, respectively, the corresponding formate [(≡SiO)4-xZr(O-C(=O)H) x] (2) and hydroxide complexes [(≡SiO)4-xZr(OH) x] (x = 1 or 2 for 3a and 3b, respectively) as major surface complexes.",

author = "Franck Rataboul and Anne Baudouin and Chlo{\'e} Thieuleux and Laurent Veyre and Christophe Cop{\'e}ret and Jean Thivolle-Cazat and Basset, {Jean Marie} and Anne Lesage and Lyndon Emsley",

year = "2004",

month = oct,

day = "6",

doi = "10.1021/ja038486h",

language = "English (US)",

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Rataboul, F, Baudouin, A, Thieuleux, C, Veyre, L, Copéret, C, Thivolle-Cazat, J, Basset, JM, Lesage, A & Emsley, L 2004, 'Molecular understanding of the formation of surface zirconium hydrides upon thermal treatment under hydrogen of [(≡SiO)Zr(CH₂tBu) ₃] by using advanced solid-state NMR techniques', Journal of the American Chemical Society, vol. 126, no. 39, pp. 12541-12550. https://doi.org/10.1021/ja038486h

Molecular understanding of the formation of surface zirconium hydrides upon thermal treatment under hydrogen of [(≡SiO)Zr(CH₂tBu) ₃] by using advanced solid-state NMR techniques. / Rataboul, Franck; Baudouin, Anne; Thieuleux, Chloé et al.
In: Journal of the American Chemical Society, Vol. 126, No. 39, 06.10.2004, p. 12541-12550.

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

TY - JOUR

T1 - Molecular understanding of the formation of surface zirconium hydrides upon thermal treatment under hydrogen of [(≡SiO)Zr(CH2tBu) 3] by using advanced solid-state NMR techniques

AU - Rataboul, Franck

AU - Baudouin, Anne

AU - Thieuleux, Chloé

AU - Veyre, Laurent

AU - Copéret, Christophe

AU - Thivolle-Cazat, Jean

AU - Basset, Jean Marie

AU - Lesage, Anne

AU - Emsley, Lyndon

PY - 2004/10/6

Y1 - 2004/10/6

N2 - The reaction of [(≡SiO)Zr(CH2tBu)3] with H 2 at 150 °C leads to the hydrogenolysis of the zirconium-carbon bonds to form a very reactive hydride intermediate(s), which further reacts with the surrounding siloxane ligands present at the surface of this support to form mainly two different zirconium hydrides: [(≡SiO)3Zr-H] (1a, 70-80%) and [(≡SiO)2ZrH2] (1b, 20-30%) along with silicon hydrides, [(≡SiO)3SiH] and [(≡SiO) 2SiH2]. Their structural identities were identified by 1H DQ solid-state NMR spectroscopy as well as reactivity studies. These two species react with CO2 and N2O to give, respectively, the corresponding formate [(≡SiO)4-xZr(O-C(=O)H) x] (2) and hydroxide complexes [(≡SiO)4-xZr(OH) x] (x = 1 or 2 for 3a and 3b, respectively) as major surface complexes.

AB - The reaction of [(≡SiO)Zr(CH2tBu)3] with H 2 at 150 °C leads to the hydrogenolysis of the zirconium-carbon bonds to form a very reactive hydride intermediate(s), which further reacts with the surrounding siloxane ligands present at the surface of this support to form mainly two different zirconium hydrides: [(≡SiO)3Zr-H] (1a, 70-80%) and [(≡SiO)2ZrH2] (1b, 20-30%) along with silicon hydrides, [(≡SiO)3SiH] and [(≡SiO) 2SiH2]. Their structural identities were identified by 1H DQ solid-state NMR spectroscopy as well as reactivity studies. These two species react with CO2 and N2O to give, respectively, the corresponding formate [(≡SiO)4-xZr(O-C(=O)H) x] (2) and hydroxide complexes [(≡SiO)4-xZr(OH) x] (x = 1 or 2 for 3a and 3b, respectively) as major surface complexes.

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U2 - 10.1021/ja038486h

DO - 10.1021/ja038486h

M3 - Article

C2 - 15453787

AN - SCOPUS:4644306523

SN - 0002-7863

VL - 126

SP - 12541

EP - 12550

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 39

ER -

Molecular understanding of the formation of surface zirconium hydrides upon thermal treatment under hydrogen of [(≡SiO)Zr(CH₂tBu) ₃] by using advanced solid-state NMR techniques

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