Modifying the reactivity in the homologation of propane by introducing aryloxide ligands on a silica supported zirconium alkyl system.
Grafting the well-defined molecular complexes [(ArO)Zr(CH2tBu)3], , and [(ArO)2Zr(CH2tBu)2], , on SiO2-(700) (ArO=2,6-Ph2C6H3O) gives the corresponding monosiloxy surface complexes [([TRIPLE BOND]SiO)Zr(CH2tBu)2(OAr)] and [([TRIPLE BOND]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 /SiO2-(700) catalytically transforms propane into its lower and higher homologues, /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.
Guillemot
Geoffroy
G
ESCPE C2P2 Equipe Chimie Organométallique de Surface (UMR 5365 CNRS/ESCPE Lyon), ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, F-69616, Villeurbanne Cedex, France.
Thieuleux
Chloé
C
Copéret
Christophe
C
Soulivong
Daravong
D
Spitzmesser
Stefan
S
Basset
Jean-Marie
JM