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Cited by 288

The DOI matches its Crossref record; 81 of the 81 references it cites were found in a registry or an index.

Metal–Ligand Bifunctional Catalysis: The “Accepted” Mechanism, the Issue of Concertedness, and the Function of the Ligand in Catalytic Cycles Involving Hydrogen Atoms

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Dub, Pavel A., Gordon, John C.·2017·ACS Catalysis
DOI 10.1021/acscatal.7b01791
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Abstract

For years, following the ideas of Shvo and Noyori, the core assumption of metal–ligand bifunctional molecular catalysis has relied on the direct involvement of the chelating ligand in the catalytic reaction via a reversible proton (H + ) transfer through cleavage/formation of one of its X–H bonds (X = O, N, C). A recently revised mechanism of the Noyori asymmetric hydrogenation reaction (Dub, P. A. et al. J. Am. Chem. Soc. 2014, 136, 3505) suggests that the ligand is rather involved in the catalytic reaction via the stabilization of determining transition states through N–H···O hydrogen-bonding interactions (HBIs) and not via a reversible H + transfer, behaving in a chemically intact manner within the productive cycle or predominantly in a chemically intact manner within productive cycles. By reexamining selected examples of computational mechanistic studies involving bifunctional catalysts from the literature in the years between 2012–2017, the purpose of this work is to point out common misconceptions in modeling concerted reactions and show that the actual stepwise nature of key transition states unveils a more complicated catalytic reaction pool (all conceivable catalytic pathways and their crossovers). Such a realization can not only potentially result in a reconsideration of the “accepted” mechanism but also lead us to a new conceptual understanding of the role that the ligand plays in the reaction. The ultimate goal of this paper is, therefore, to encourage the reader to reconsider the function of the ligand in catalytic cycles of hydrogenation/dehydrogenation with bifunctional catalysts, which until recently has relied almost exclusively on a chemically noninnocent ligand.

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Metadata

Authors
Dub, P. A., & Gordon, J. C.
Venue
ACS Catalysis
Publisher
American Chemical Society (ACS)
Published
2017-09-01
Volume
7
Issue
10
Pages
6635-6655
ISSN
2155-5435 (ISSN-L)
DOI
10.1021/acscatal.7b01791
OpenAlex
W2745393560
Cited by
288
References
81
FWCI
13.29
Type
journal article
Language
en
Open access
green

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