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research article

Supramolecular triruthenium cluster-based benzene hydrogenation catalysis: Fact or fiction?

Hagen, CM
•
Vieille-Petit, L
•
Laurenczy, G  
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2005
Organometallics

The question is addressed of whether the triruthenium cluster cation Ru-3(mu(2)-H)(3)(eta(6)C(6)H(6))(eta(6)-C6Me6)(2)(mu(3)-O), 1, is a supramolecular, outer-sphere benzene hydrogenation catalyst or is 1 a precatalyst to well-known Ru(0)(n) catalysis of benzene hydrogenation. This question of "is it homogeneous or heterogeneous catalysis?" is especially important in the present case since if 1 is a supramolecular, homogeneous catalyst as postulated in the literature that is, if 1 can in fact accomplish catalysis of reactions as difficult as benzene reduction with no inner-sphere, d-orbital-mediated ligand dissociation, oxidative addition, migratory insertion, or reductive elimination-then that finding holds promise of rewriting the rules of organometallic-based catalysis. The identity of the true catalyst derived from 1 is, therefore, addressed by a collaborative effort between research groups at the Universite de Neuchatel and Colorado State University. The methodology employed is that worked out previously for addressing the historically vexing question of "is it homogeneous or heterogeneous catalysis?" (Lin, Y.; Finke, R. G. Inorg. Chem. 1994, 33, 489 1). A combination of the following classes of experiments have been employed: (i) Ru metal product studies; (ii) kinetic studies; (iii) Hg(0) and quantitative poisoning experiments, (iv) NMR studies of H/D exchange rates; (v) other data, plus (vi) the principle that the correct mechanism will explain all of the data. The results provide a compelling case that 1 is not the true benzene hydrogenation catalyst as previously believed; instead, all our evidence is consistent with, and supportive of, trace Ru(0) derived from 1 under the reaction conditions as the true, active catalyst. Nine additional conclusions are also presented as part of the summary and take-home messages, as well as a citation of "Halpern's rules" for catalysis.

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Type
research article
DOI
10.1021/om048976y
Web of Science ID

WOS:000228191400008

Author(s)
Hagen, CM
Vieille-Petit, L
Laurenczy, G  
Suss-Fink, G
Finke, RG
Date Issued

2005

Published in
Organometallics
Volume

24

Issue

8

Start page

1819

End page

1831

Subjects

transition-metal nanoclusters

•

ring-opening metathesis

•

ligandbifunctional catalysis

•

stabilized rh(0) nanoclusters

•

autocatalyticsurface-growth

•

electron-transfer reactions

•

liquid-phasehydrogenation

•

phosphine-borane adducts

•

aqueous salt solution

•

heterogeneous catalysis

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCOM  
Available on Infoscience
November 9, 2005
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/219926
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