Modifying the reactivity in the homologation of propane by introducing aryloxide ligands on a silica supported zirconium alkyl system

Geoffroy Guillemot; Chloé Thieuleux; Christophe Copéret; Daravong Soulivong; Stefan Spitzmesser; Jean Marie Basset

doi:10.1039/b708883c

Modifying the reactivity in the homologation of propane by introducing aryloxide ligands on a silica supported zirconium alkyl system

Geoffroy Guillemot, Chloé Thieuleux^*, Christophe Copéret, Daravong Soulivong, Stefan Spitzmesser, Jean Marie Basset

^*Corresponding author for this work

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

6 Scopus citations

Abstract

Grafting the well-defined molecular complexes [(ArO)Zr(CH ₂tBu)₃], 2, and [(ArO)₂Zr(CH ₂tBu)₂], 3, on SiO_2-(700) (ArO = 2,6-Ph ₂C₆H₃O) gives the corresponding monosiloxy surface complexes [(≡SiO)Zr(CH₂tBu)₂(OAr)] and [(≡SiO)Zr(CH₂tBu)(OAr)₂] as major surface species as evidenced by mass balance analysis, IR and NMR spectroscopies. In both cases, minor cyclometallated species (ca. 20%) are also probably formed during the grafting process. While 2/SiO_2-(700) catalytically transforms propane into its lower and higher homologues, 3/SiO_2-(700) remains inactive. Moreover, the formation of butane as the major higher homologues is consistent with the formation of metallocarbene intermediates in this system in contrast to what was observed for the corresponding homologation reaction on silica supported zirconium hydrides.

Original language	English (US)
Pages (from-to)	4589-4593
Number of pages	5
Journal	Dalton transactions
Issue number	40
DOIs	https://doi.org/10.1039/b708883c
State	Published - 2007
Externally published	Yes

ASJC Scopus subject areas

Inorganic Chemistry

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@article{66e98e107b544b72aad8d634a6983a80,

title = "Modifying the reactivity in the homologation of propane by introducing aryloxide ligands on a silica supported zirconium alkyl system",

abstract = "Grafting the well-defined molecular complexes [(ArO)Zr(CH 2tBu)3], 2, and [(ArO)2Zr(CH 2tBu)2], 3, on SiO2-(700) (ArO = 2,6-Ph 2C6H3O) gives the corresponding monosiloxy surface complexes [(≡SiO)Zr(CH2tBu)2(OAr)] and [(≡SiO)Zr(CH2tBu)(OAr)2] as major surface species as evidenced by mass balance analysis, IR and NMR spectroscopies. In both cases, minor cyclometallated species (ca. 20%) are also probably formed during the grafting process. While 2/SiO2-(700) catalytically transforms propane into its lower and higher homologues, 3/SiO2-(700) remains inactive. Moreover, the formation of butane as the major higher homologues is consistent with the formation of metallocarbene intermediates in this system in contrast to what was observed for the corresponding homologation reaction on silica supported zirconium hydrides.",

author = "Geoffroy Guillemot and Chlo{\'e} Thieuleux and Christophe Cop{\'e}ret and Daravong Soulivong and Stefan Spitzmesser and Basset, {Jean Marie}",

year = "2007",

doi = "10.1039/b708883c",

language = "English (US)",

pages = "4589--4593",

journal = "Dalton transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "40",

}

TY - JOUR

T1 - Modifying the reactivity in the homologation of propane by introducing aryloxide ligands on a silica supported zirconium alkyl system

AU - Guillemot, Geoffroy

AU - Thieuleux, Chloé

AU - Copéret, Christophe

AU - Soulivong, Daravong

AU - Spitzmesser, Stefan

AU - Basset, Jean Marie

PY - 2007

Y1 - 2007

N2 - Grafting the well-defined molecular complexes [(ArO)Zr(CH 2tBu)3], 2, and [(ArO)2Zr(CH 2tBu)2], 3, on SiO2-(700) (ArO = 2,6-Ph 2C6H3O) gives the corresponding monosiloxy surface complexes [(≡SiO)Zr(CH2tBu)2(OAr)] and [(≡SiO)Zr(CH2tBu)(OAr)2] as major surface species as evidenced by mass balance analysis, IR and NMR spectroscopies. In both cases, minor cyclometallated species (ca. 20%) are also probably formed during the grafting process. While 2/SiO2-(700) catalytically transforms propane into its lower and higher homologues, 3/SiO2-(700) remains inactive. Moreover, the formation of butane as the major higher homologues is consistent with the formation of metallocarbene intermediates in this system in contrast to what was observed for the corresponding homologation reaction on silica supported zirconium hydrides.

AB - Grafting the well-defined molecular complexes [(ArO)Zr(CH 2tBu)3], 2, and [(ArO)2Zr(CH 2tBu)2], 3, on SiO2-(700) (ArO = 2,6-Ph 2C6H3O) gives the corresponding monosiloxy surface complexes [(≡SiO)Zr(CH2tBu)2(OAr)] and [(≡SiO)Zr(CH2tBu)(OAr)2] as major surface species as evidenced by mass balance analysis, IR and NMR spectroscopies. In both cases, minor cyclometallated species (ca. 20%) are also probably formed during the grafting process. While 2/SiO2-(700) catalytically transforms propane into its lower and higher homologues, 3/SiO2-(700) remains inactive. Moreover, the formation of butane as the major higher homologues is consistent with the formation of metallocarbene intermediates in this system in contrast to what was observed for the corresponding homologation reaction on silica supported zirconium hydrides.

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U2 - 10.1039/b708883c

DO - 10.1039/b708883c

M3 - Article

AN - SCOPUS:35148837500

SN - 1477-9226

SP - 4589

EP - 4593

JO - Dalton transactions

JF - Dalton transactions

IS - 40

ER -

Modifying the reactivity in the homologation of propane by introducing aryloxide ligands on a silica supported zirconium alkyl system

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