Computational Characterization of Bidentate P-Donor Ligands: Direct Comparison to Tolman's Electronic Parameters

Tímea R Kégl; Noémi Pálinkás; László Kollár; Tamás Kégl

doi:10.3390/molecules23123176

Computational Characterization of Bidentate P-Donor Ligands: Direct Comparison to Tolman's Electronic Parameters

Molecules. 2018 Dec 1;23(12):3176. doi: 10.3390/molecules23123176.

Authors

Tímea R Kégl¹, Noémi Pálinkás², László Kollár³, Tamás Kégl⁴

Affiliations

¹ Department of Inorganic Chemistry and MTA-PTE Research Group for Selective Chemical Syntheses, University of Pécs, H-7622 Pécs, Hungary. timea.kegl@gmail.com.
² Department of Inorganic Chemistry, University of Pécs, H-7622 Pécs, Hungary. noemi.palinkas@gmail.com.
³ Department of Inorganic Chemistry and MTA-PTE Research Group for Selective Chemical Syntheses, University of Pécs, H-7622 Pécs, Hungary. kollar@gamma.ttk.pte.hu.
⁴ Department of Inorganic Chemistry and MTA-PTE Research Group for Selective Chemical Syntheses, University of Pécs, H-7622 Pécs, Hungary. tkegl@gamma.ttk.pte.hu.

Abstract

The applicability of two types of transition-metal carbonyl complexes as appropriate candidates for computationally derived Tolman's ligand electronic parameters were examined with density functional theory (DFT) calculations employing the B97D3 functional. Both Pd⁽⁰⁾L2(CO) and HRh^(I)L2(CO) complexes correlated well with the experimental Tolman Electronic Parameter scale. For direct comparison of the electronic effects of diphosphines with those of monophosphines, the palladium-containing system is recommended. The t r a n s influence of various phosphines did not show a major difference, but the decrease of the H-Rh-P angle from linear can cause a significant change.

Keywords: DFT; QTAIM; diphosphines; electronic parameters.

MeSH terms

Algorithms
Density Functional Theory
Ligands
Models, Chemical*
Models, Molecular
Phosphines / chemistry*
Structure-Activity Relationship

Substances

Ligands
Phosphines