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Viable pathways for the oxidative addition of iodobenzene to palladium(0)-triphenylphosphinecarbonyl complexes: a theoretical study

PĂĄlinkĂĄs, NoĂŠmi

KollĂĄr, LĂĄszlĂł

KĂŠgl, TamĂĄs

Royal Society of Chemistry

2017-10

QD Chemistry / kĂŠmia

The oxidative addition of 4-substituted iodobenzenes on Pd(0) catalysts under CO atmosphere was investigated
by means of density functional calculations employing the M06//B97-D3 level of theory. The
18-electron triphenylphosphine-tricarbonyl complex was found to be the global minimum. Several coordinatively
unsaturated species are predicted to be present both in N,N-dimethylformamide and toluene
solution. In terms of activating iodobenzene, bis(triphenylphosphine)palladium(0) was proved to be the
most active. However, due to its lower thermodynamic stability, it is slightly inferior to the Pd-triphenylphosphine-
carbonyl complex, which is predicted to react with a free energy of activation of 23.2
kcal mol−1 with respect to the initial resting state tetrakis(triphenylphosphine)palladium(0). The effect of
4-substituents of iodobenzene on reaction energetics is also discussed. The activity of the Pd(0) catalyst
was found to be governed by the donor–acceptor strength of the ancillary ligands: the barrier decreases
with increasing basicity and decreasing back-donating capability.

magyar

Article

PeerReviewed

info:eu-repo/semantics/article

text

http://real.mtak.hu/74366/1/dalton_2017_15789.pdf

PĂĄlinkĂĄs, NoĂŠmi and KollĂĄr, LĂĄszlĂł and KĂŠgl, TamĂĄs (2017) Viable pathways for the oxidative addition of iodobenzene to palladium(0)-triphenylphosphinecarbonyl complexes: a theoretical study. DALTON TRANSACTIONS, 46. pp. 15789-15802. ISSN 1477-9226

http://real.mtak.hu/74366/

https://doi.org/10.1039/c7dt03642f