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Unravelling strong temperature-dependence of JHD in transition metal hydrides : solvation and non-covalent interactions versus temperature-elastic H-H bonds

Polukeev, Alexey V. LU ; Capelli, Silvia C. and Wendt, Ola F. LU (2023) In Chemical Science 14(43). p.12308-12320
Abstract

A number of transition metal hydrides reveal intriguing temperature-dependent JHD in their deuterated derivatives and possibly the temperature dependent hydrogen-hydrogen distance (r(H-H)) as well. Previously, theoretical studies rationalized JHD and r(H-H) changes in such compounds through a “temperature-elastic” structure model with a significant population of vibrational states in an anharmonic potential. Based on the first variable temperature neutron diffraction study of a relevant complex, (p-H-POCOP)IrH2, observation of its elusive counterpart with longer r(H-H), crystallized as an adduct with C6F5I, and thorough spectroscopic and computational study, we argue that the model... (More)

A number of transition metal hydrides reveal intriguing temperature-dependent JHD in their deuterated derivatives and possibly the temperature dependent hydrogen-hydrogen distance (r(H-H)) as well. Previously, theoretical studies rationalized JHD and r(H-H) changes in such compounds through a “temperature-elastic” structure model with a significant population of vibrational states in an anharmonic potential. Based on the first variable temperature neutron diffraction study of a relevant complex, (p-H-POCOP)IrH2, observation of its elusive counterpart with longer r(H-H), crystallized as an adduct with C6F5I, and thorough spectroscopic and computational study, we argue that the model involving isomeric species in solution at least in some cases is more relevant. The existence of such isomers is enabled or enhanced by solvation and weak non-covalent interactions with solvent, such as halogen or dihydrogen bonds. “Non-classical” hydrides with r(H-H) ≈ 1.0-1.6 Å are especially sensitive to the above-mentioned factors.

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author
; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Chemical Science
volume
14
issue
43
pages
13 pages
publisher
Royal Society of Chemistry
external identifiers
  • pmid:37969611
  • scopus:85175248762
ISSN
2041-6520
DOI
10.1039/d3sc04197b
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2023 The Royal Society of Chemistry
id
eea148a7-d8b8-42a6-a341-fb049a71475a
date added to LUP
2023-12-14 15:22:18
date last changed
2024-04-13 07:30:02
@article{eea148a7-d8b8-42a6-a341-fb049a71475a,
  abstract     = {{<p>A number of transition metal hydrides reveal intriguing temperature-dependent J<sub>HD</sub> in their deuterated derivatives and possibly the temperature dependent hydrogen-hydrogen distance (r(H-H)) as well. Previously, theoretical studies rationalized J<sub>HD</sub> and r(H-H) changes in such compounds through a “temperature-elastic” structure model with a significant population of vibrational states in an anharmonic potential. Based on the first variable temperature neutron diffraction study of a relevant complex, (p-H-POCOP)IrH<sub>2</sub>, observation of its elusive counterpart with longer r(H-H), crystallized as an adduct with C<sub>6</sub>F<sub>5</sub>I, and thorough spectroscopic and computational study, we argue that the model involving isomeric species in solution at least in some cases is more relevant. The existence of such isomers is enabled or enhanced by solvation and weak non-covalent interactions with solvent, such as halogen or dihydrogen bonds. “Non-classical” hydrides with r(H-H) ≈ 1.0-1.6 Å are especially sensitive to the above-mentioned factors.</p>}},
  author       = {{Polukeev, Alexey V. and Capelli, Silvia C. and Wendt, Ola F.}},
  issn         = {{2041-6520}},
  language     = {{eng}},
  month        = {{10}},
  number       = {{43}},
  pages        = {{12308--12320}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Chemical Science}},
  title        = {{Unravelling strong temperature-dependence of J<sub>HD</sub> in transition metal hydrides : solvation and non-covalent interactions versus temperature-elastic H-H bonds}},
  url          = {{http://dx.doi.org/10.1039/d3sc04197b}},
  doi          = {{10.1039/d3sc04197b}},
  volume       = {{14}},
  year         = {{2023}},
}