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The acetate proton shuttle between mutually trans ligands

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Title: The acetate proton shuttle between mutually trans ligands
Authors: De Aguirre, A
Diez-Gonzalez, S
Maseras, F
Martin, M
Sola, E
Item Type: Journal Article
Abstract: This work addresses a counterintuitive observation in the reactivity of the well-known ruthenium complexes [Ru(X)H(CO)(PiPr3)2], according to which the 5-coordinate chloro complex (X = Cl, 1) is less reactive toward phenylacetylene than its 6-coordinate acetate analogue (X = κO2-OC(O)Me, 3), since 3 undergoes a hydride-to-alkenyl-to-alkynyl transformation, whereas the reaction of 1 stops at the alkenyl derivative. The experimental kinetics of the key alkenyl-to-alkynyl step in the acetate complex are compared to the results of DFT calculations, which disclose the ability of the acetate not only to assist the alkyne C–H activation step via a CMD mechanism but also to subsequently deliver the proton to the alkenyl ligand. Possible consequences of this mechanistic resource connecting mutually trans ligands are briefly discussed on the basis of reported chemoselectivity changes induced by carboxylate ligands in 1-alkyne hydrosilylations catalyzed by this type of ruthenium complexes.
Issue Date: 13-Aug-2018
Date of Acceptance: 1-Jul-2018
URI: http://hdl.handle.net/10044/1/62039
DOI: https://dx.doi.org/10.1021/acs.organomet.8b00417
ISSN: 0276-7333
Publisher: American Chemical Society
Start Page: 2645
End Page: 2651
Journal / Book Title: Organometallics
Volume: 37
Issue: 15
Copyright Statement: © 2018 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acs.organomet.8b00417
Keywords: Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Chemistry
MOLECULAR-ORBITAL METHODS
RUTHENIUM-CATALYZED HYDROSILYLATION
C-H ACTIVATION
INSERTION REACTIONS
ALKYNYL COMPLEXES
DIRECT ARYLATION
BASIS-SETS
BOND
MECHANISM
ALKENYL
0302 Inorganic Chemistry
0305 Organic Chemistry
0399 Other Chemical Sciences
Organic Chemistry
Publication Status: Published
Online Publication Date: 2018-07-30
Appears in Collections:Chemistry
Catalysis and Advanced Materials
Faculty of Natural Sciences



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