TY - JOUR
T1 - Spectroscopically distinct sites present in methyltrioxorhenium grafted onto silica-alumina, and their abilities to initiate olefin metathesis
AU - Moses, Anthony W.
AU - Raab, Christina
AU - Nelson, Ryan C.
AU - Leifeste, Heather D.
AU - Ramsahye, Naseem A.
AU - Chattopadhyay, Swarup
AU - Eckert, Juergen
AU - Chmelka, Bradley F.
AU - Scott, Susannah L.
PY - 2007/7/18
Y1 - 2007/7/18
N2 - Deposition of CH3ReO3 onto the surface of dehydrated, amorphous silica-alumina generates a highly active, supported catalyst for the metathesis of olefins. However, silica-alumina with a high (10 wt %) Re loading is no more active than silica-alumina with low (1 wt %)Joading, while CH 3ReO3 on silica is completely inactive. Catalysts prepared by grafting CH3ReO3 on silica-alumina contain two types of spectroscopically distinct sites. The more strongly bound sites are responsible for olefin metathesis activity and are formed preferentially at low Re loadings (≤1 wt %). They are created by two Lewis acid/base interactions: (1) the coordination of an oxo ligand to an Al center of the support and (2) interaction of one of the adjacent bridging oxygens (AlOSi) with the Re center. At higher Re loadings (1-10 wt%), CH3ReO3 also interacts with surface silanols by H-bonding. This gives rise to highly mobile sites, most of which can be observed by 13C solid-state NMR even without magic-angle spinning. Their formation can be prevented by capping the surface hydroxyl groups with hexamethyldisilazane prior to grafting CH 3ReO3, resulting in a metathesis catalyst that is more selective, more robust, and more efficient in terms of Re use.
AB - Deposition of CH3ReO3 onto the surface of dehydrated, amorphous silica-alumina generates a highly active, supported catalyst for the metathesis of olefins. However, silica-alumina with a high (10 wt %) Re loading is no more active than silica-alumina with low (1 wt %)Joading, while CH 3ReO3 on silica is completely inactive. Catalysts prepared by grafting CH3ReO3 on silica-alumina contain two types of spectroscopically distinct sites. The more strongly bound sites are responsible for olefin metathesis activity and are formed preferentially at low Re loadings (≤1 wt %). They are created by two Lewis acid/base interactions: (1) the coordination of an oxo ligand to an Al center of the support and (2) interaction of one of the adjacent bridging oxygens (AlOSi) with the Re center. At higher Re loadings (1-10 wt%), CH3ReO3 also interacts with surface silanols by H-bonding. This gives rise to highly mobile sites, most of which can be observed by 13C solid-state NMR even without magic-angle spinning. Their formation can be prevented by capping the surface hydroxyl groups with hexamethyldisilazane prior to grafting CH 3ReO3, resulting in a metathesis catalyst that is more selective, more robust, and more efficient in terms of Re use.
UR - http://www.scopus.com/inward/record.url?scp=34848880748&partnerID=8YFLogxK
U2 - 10.1021/ja072707s
DO - 10.1021/ja072707s
M3 - Article
C2 - 17595088
AN - SCOPUS:34848880748
VL - 129
SP - 8912
EP - 8920
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 28
ER -