%0 Generic
%A Škríba, Anton
%A Jašík, Juraj
%A Andris, Erik
%A Roithová, Jana
%D 2016
%T Interaction of Ruthenium(II) with Terminal Alkynes:
Benchmarking DFT Methods with Spectroscopic Data
%U https://acs.figshare.com/articles/dataset/Interaction_of_Ruthenium_II_with_Terminal_Alkynes_Benchmarking_DFT_Methods_with_Spectroscopic_Data/3121297
%R 10.1021/acs.organomet.6b00021.s002
%2 https://acs.figshare.com/ndownloader/files/4855801
%K Terminal Alkynes
%K BP
%K activation
%K ruthenium catalysis
%K DFT functionals
%K bond
%K PBEPBE
%K e.g
%K Benchmarking DFT Methods
%K IRPD spectrum
%K vinylidene form
%K organometallic complexes
%K GGA methods
%K DFT methods
%K B 3LYP
%K terminal alkyne
%K Spectroscopic Data Helium
%K meta GGA functionals
%X Helium
tagging infrared photodissociation (IRPD) spectroscopy for the characterization
of organometallic complexes is presented. The IRPD spectrum of the
[RuCp(PPh3)(PhCCH)]+ complex reveals that
more than 80% of the detected ions correspond to a structure with
π-coordinated phenylacetylene, and the rest are complexes with
the alkyne probably isomerized to its vinylidene form. The detected
CC and C–H stretches of the terminal alkyne reflect
the degree of activation of the triple bond. They are used to benchmark
the popular DFT functionals used in theoretical studies of ruthenium
catalysis. It is shown that there are only small differences between
the methods. GGA methods (e.g., BP86 or PBEPBE) and (hybrid) meta
GGA functionals (e.g., M06) provide slightly better descriptions of
this system than hybrid DFT methods such as B3LYP. A notable exception
is M06-2X, which significantly underestimates the activation of the
CC bond by the coordination to the ruthenium complex.
%I ACS Publications