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Immobilization and Characterization of RuCl2(PPh3)(3) Mesoporous Silica SBA-3

Grünberg, A. and Gutmann, T. and Rothermel, N. and Xu, Y. P. and Breitzke, H. and Buntkowsky, G. :
Immobilization and Characterization of RuCl2(PPh3)(3) Mesoporous Silica SBA-3.
[Online-Edition: <Go to ISI>://WOS:000322050200013]
In: Zeitschrift Fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics, 227 (6-7) pp. 901-915.
[Article] , (2013)

Official URL: <Go to ISI>://WOS:000322050200013

Abstract

The five-fold coordinated ruthenium (II) catalyst RuCl2(PPh3)(3) is heterogenized on the surface of amine functionalized mesoporous silica material SBA-3 and studied by BET, XRD and P-31 CP-MAS solid-state NMR. The spectra indicate the replacement of one or two of the triphenyl-phosphine groups in the course of the grafting. To distinguish between both possibilities two-dimensional J-resolved P-31 MAS solid-state NMR combined with quantum chemical calculations is employed. The changes of the scalar coupling pattern between the neat catalyst and the immobilized catalyst suggest the replacement of two of the PPh3-groups by coordinative bonds to the amine-functions of the linker. DFT calculations reveal the absence of two chemically and magnetically equivalent phosphines and confirm the replacement of two PPh3-groups. This finding is similar to the results observed for the binding of the rhodium in the Wilkinson's catalyst, despite the different coordination of the metals (four-fold versus five-fold), the presence of two chlorine ligands and the different transition metal.

Item Type: Article
Erschienen: 2013
Creators: Grünberg, A. and Gutmann, T. and Rothermel, N. and Xu, Y. P. and Breitzke, H. and Buntkowsky, G.
Title: Immobilization and Characterization of RuCl2(PPh3)(3) Mesoporous Silica SBA-3
Language: German
Abstract:

The five-fold coordinated ruthenium (II) catalyst RuCl2(PPh3)(3) is heterogenized on the surface of amine functionalized mesoporous silica material SBA-3 and studied by BET, XRD and P-31 CP-MAS solid-state NMR. The spectra indicate the replacement of one or two of the triphenyl-phosphine groups in the course of the grafting. To distinguish between both possibilities two-dimensional J-resolved P-31 MAS solid-state NMR combined with quantum chemical calculations is employed. The changes of the scalar coupling pattern between the neat catalyst and the immobilized catalyst suggest the replacement of two of the PPh3-groups by coordinative bonds to the amine-functions of the linker. DFT calculations reveal the absence of two chemically and magnetically equivalent phosphines and confirm the replacement of two PPh3-groups. This finding is similar to the results observed for the binding of the rhodium in the Wilkinson's catalyst, despite the different coordination of the metals (four-fold versus five-fold), the presence of two chlorine ligands and the different transition metal.

Journal or Publication Title: Zeitschrift Fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics
Volume: 227
Number: 6-7
Uncontrolled Keywords: rucl2(pph3)(3) heterogeneous catalysis solid-state-nmr mas scalar interactions quantum-chemical calculations solid-state nmr cyclohexene hydroformylation sio2-tethered catalyst dihydrogen complexes phosphine complexes wilkinsons complex metal-complexes 1st observation hydrogenation oxidation
Divisions: 07 Fachbereich Chemie > Physical Chemistry
07 Fachbereich Chemie
Date Deposited: 27 Oct 2014 20:41
Official URL: <Go to ISI>://WOS:000322050200013
Additional Information:

186NB Times Cited:1 Cited References Count:67

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