Repository logo

Infoscience

  • English
  • French
Log In
Logo EPFL, École polytechnique fédérale de Lausanne

Infoscience

  • English
  • French
Log In
  1. Home
  2. Academic and Research Output
  3. Journal articles
  4. Bipodal Surface Organometallic Complexes with Surface N-Donor Ligands and Application to the Catalytic Cleavage of C-H and C-C Bonds in n-Butane
 
Loading...
Thumbnail Image
research article

Bipodal Surface Organometallic Complexes with Surface N-Donor Ligands and Application to the Catalytic Cleavage of C-H and C-C Bonds in n-Butane

Bendjeriou-Sedjerari, Anissa
•
Azzi, Joachim M.
•
Abou-Hamad, Edy
Show more
2013
Journal of the American Chemical Society

We present a new generation of ``true vicinal'' functions well-distributed on the inner surface of SBA15: [( Si-NH2)( Si-OH)] (1) and [( Si-NH2)(2)] (2). From these amine-modified SBA15s, two new well-defined surface organometallic species [( Si-NH-)( Si-O-)]Zr-(CH(2)tBu)(2) (3) and [( Si-NH-)(2)]Zr(CH(2)tBu)(2) (4) have been obtained by reaction with Zr(CH(2)tBu)(4). The surfaces were characterized with 2D multiple-quantum H-1-H-1 NMR and infrared spectroscopies. Energy-filtered transmission electron microscopy (EFTEM), mass balance, and elemental analysis unambiguously proved that Zr(CH(2)tBu)(4) reacts with these vicinal amine-modified surfaces to give mainly bipodal bis(neopentyl)zirconium complexes (3) and (4), uniformly distributed in the channels of SBA15. (3) and (4) react with hydrogen to give the homologous hydrides (5) and (6). Hydrogenolysis of n-butane catalyzed by these hydrides was carried out at low temperature (100 degrees C) and low pressure (1 atm). While (6) exhibits a bis(silylamido)zirconium bishydride, [( Si-NH-)(2)]Zr(H)(2) (6a) (60%), and a bis(silylamido)silyloxozirconium monohydride, [( Si-NH-)(2)(Si-O-)]ZrH (6b) (40%), (5) displays a new surface organometallic complex characterized by an H-1 NMR signal at 14.46 ppm. The latter is assigned to a (silylimido)(silyloxo)zirconium monohydride, [( Si-N=)( Si-O-)]ZrH (5b) (30%), coexistent with a (silylamido)(silyloxo)zirconium bishydride, [( Si-NH-) ( Si-O-)]Zr(H)(2) (5a) (45%), and a silylamidobis(silyloxo)zirconium monohydride, [( Si-NH-)( Si-O-)(2)]ZrH (5c) (25%). Surprisingly, nitrogen surface ligands possess catalytic properties already encountered with silicon oxide surfaces, but interestingly, catalyst (5) with chelating [N,O] shows better activity than (6) with chelating [N,N].

  • Details
  • Metrics
Type
research article
DOI
10.1021/ja407902g
Web of Science ID

WOS:000328099400046

Author(s)
Bendjeriou-Sedjerari, Anissa
•
Azzi, Joachim M.
•
Abou-Hamad, Edy
•
Anjum, Dalaver H.
•
Pasha, Fahran A.
•
Huang, Kuo-Wei
•
Emsley, Lyndon  
•
Basset, Jean-Marie
Date Issued

2013

Publisher

AMER CHEMICAL SOC

Published in
Journal of the American Chemical Society
Volume

135

Issue

47

Start page

17943

End page

17951

Peer reviewed

REVIEWED

Written at

OTHER

EPFL units
LRM  
Available on Infoscience
January 8, 2015
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/109960
Logo EPFL, École polytechnique fédérale de Lausanne
  • Contact
  • infoscience@epfl.ch

  • Follow us on Facebook
  • Follow us on Instagram
  • Follow us on LinkedIn
  • Follow us on X
  • Follow us on Youtube
AccessibilityLegal noticePrivacy policyCookie settingsEnd User AgreementGet helpFeedback

Infoscience is a service managed and provided by the Library and IT Services of EPFL. © EPFL, tous droits réservés