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

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.

SUBMITTER: Kegl TR

PROVIDER: S-EPMC6321482 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

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

Kégl Tímea R TR Pálinkás Noémi N Kollár László L Kégl Tamás T

Molecules (Basel, Switzerland) 20181201 12

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<sup>(0)</sup>L2(CO) and HRh<sup>(I)</sup>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 palla ...[more]

PMID: 30513796

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