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

Pálinkás, Noémi and Kollár, László and Kégl, Tamás (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

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Abstract

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.

Item Type: Article
Subjects: Q Science / természettudomány > QD Chemistry / kémia
Depositing User: Pap Viktória
Date Deposited: 13 Feb 2018 08:04
Last Modified: 13 Feb 2018 08:04
URI: http://real.mtak.hu/id/eprint/74366

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