Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis
AuthorsHamieh, Ali Imad Ali
KAUST DepartmentAli I. Al-Naimi Petroleum Engineering Research Center (ANPERC)
Chemical Science Program
KAUST Catalysis Center (KCC)
KAUST Solar Center (KSC)
Physical Science and Engineering (PSE) Division
Online Publication Date2016-07-28
Print Publication Date2016-08-08
Permanent link to this recordhttp://hdl.handle.net/10754/621681
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AbstractAn efficient and potentially scalable method is described for the synthesis of the silica-supported complexes [(≡Si-O-)WMe5] and [(≡Si-O-)WMe2(≡CH)] obtained by in situ alkylation of the surface-grafted tungsten chloride [(≡Si-O-)WCl5] (1). [(≡Si-O-)WCl5] can be readily prepared by the reaction of commercially available and stable tungsten hexachloride WCl6 with partially dehydroxylated silica at 700 °C (SiO2-700). Further reaction with ZnMe2 at room temperature rapidly forms a mixture of surface-alkylated tungsten complexes. They were fully characterized by microanalysis, FTIR, mass balance, and solid-state NMR (1H, 13C, 1H-13C HETCOR, 1H-1H double quantum and triple quantum) and identified as [(≡Si-O-)WMe5] and another product, [(≡Si-O-)WMe2(≡CH)]. The latter might have been generated by partial decomposition of the tungsten methyl chloride compound, which is formed during the stepwise alkylation of [(≡Si-O-)WCl5]. DFT calculations were carried out to check the relative stability of the tungsten methyl chloride intermediates and the feasibility of the reaction and corroborate the experimental results. This tungsten complex and its derivative were found to be active catalysts for the metathesis of cyclooctane. © 2016 American Chemical Society.
CitationHamieh A, Dey R, Samantaray MK, Abdel-Azeim S, Abou-Hamad E, et al. (2016) Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis. Organometallics 35: 2524–2531. Available: http://dx.doi.org/10.1021/acs.organomet.6b00432.
SponsorsThis work was supported by the funds from the King Abdullah University of Science and Technology (KAUST).
PublisherAmerican Chemical Society (ACS)