Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane
Type
ArticleAuthors
Samantaray, ManojaKavitake, Santosh Giridhar
Morlanes, Natalia Sanchez

Abou-Hamad, Edy

Hamieh, Ali Imad Ali

Dey, Raju

Basset, Jean-Marie

KAUST Department
Ali I. Al-Naimi Petroleum Engineering Research Center (ANPERC)Chemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2017-02-23Online Publication Date
2017-02-23Print Publication Date
2017-03-08Permanent link to this record
http://hdl.handle.net/10754/623929
Metadata
Show full item recordAbstract
Two compatible organometallic complexes, W(Me)(6) (1) and TiNp4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO2-700) to synthesize the well-defined bimetallic precatalyst [(equivalent to Si-O-)W(Me)(5)(equivalent to Si-O-)Ti(Np)(3)] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in H-1-H-1 multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(equivalent to Si-O-)W(Me)(5)] (3), with a TON of 98, for propane metathesis at 150 degrees C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by beta-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 degrees C) using a well-defined bimetallic system prepared via the SOMC approach.Citation
Samantaray MK, Kavitake S, Morlanés N, Abou-Hamad E, Hamieh A, et al. (2017) Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane. Journal of the American Chemical Society 139: 3522–3527. Available: http://dx.doi.org/10.1021/jacs.6b12970.Sponsors
The authors acknowledge the KAUST Nuclear Magnetic Resonance Core Lab and Analytical Core Lab (ACL) for the analysis of the sample. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR).Publisher
American Chemical Society (ACS)Additional Links
http://pubs.acs.org/doi/abs/10.1021/jacs.6b12970ae974a485f413a2113503eed53cd6c53
10.1021/jacs.6b12970