Selective C-H activation at a molecular rhodium sigma-alkane complex by solid/gas single-crystal to single-crystal H/D exchange
File(s)
Published version
Author(s)
Type
Journal Article
Abstract
The controlled catalytic functionalization of alkanes via the activation of C–H bonds is a significant challenge. Although C–H activation by transition metal catalysts is often suggested to operate via intermediate σ-alkane complexes, such transient species are difficult to observe due to their instability in solution. This instability may be controlled by use of solid/gas synthetic techniques that enable the isolation of single-crystals of well-defined σ-alkane complexes. Here we show that, using this unique platform, selective alkane C–H activation occurs, as probed by H/D exchange using D2, and that five different isotopomers/isotopologues of the σ-alkane complex result, as characterized by single-crystal neutron diffraction studies for three examples. Low-energy fluxional processes associated with the σ-alkane ligand are identified using variable-temperature X-ray diffraction, solid-state NMR spectroscopy, and periodic DFT calculations. These observations connect σ-alkane complexes with their C–H activated products, and demonstrate that alkane-ligand mobility, and selective C–H activation, are possible when these processes occur in the constrained environment of the solid-state.
Date Issued
2016-09-15
Date Acceptance
2016-09-01
Citation
Journal of the American Chemical Society, 2016, 138 (40), pp.13369-13378
ISSN
0002-7863
Publisher
American Chemical Society
Start Page
13369
End Page
13378
Journal / Book Title
Journal of the American Chemical Society
Volume
138
Issue
40
Copyright Statement
© 2016 American Chemical Society. This is an open access article published under a Creative Commons Attribution (CC-BY)
License, which permits unrestricted use, distribution and reproduction in any medium,
provided the author and source are cited.
License, which permits unrestricted use, distribution and reproduction in any medium,
provided the author and source are cited.
License URL
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000385469600043&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
METAL OXIDE CLUSTERS
TIME-RESOLVED IR
DEHYDROGENATION-OLEFIN-METATHESIS
ORGANOMETALLIC CHEMISTRY
NEUTRON-DIFFRACTION
STATE NMR
X-RAY
CATALYTIC-HYDROGENATION
TRANSITION-METALS
ETHANE COMPLEXES
Publication Status
Published
Date Publish Online
2016-10-03