Reactivity of [Rh(β-diketonato)(cod)] complexes: A DFT approach

Conradie, Jeanet

doi:10.1016/j.jorganchem.2012.08.015

Cited by 11 publications

(3 citation statements)

References 52 publications

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“…The first irreversible anodic oxidation peak is assigned to the oxidation of Rh(I) to Rh(III), and the second reversible couple is assigned to the one-electron transfer process of the ferrocenyl group of the (FcCOCHCOCF 3 ) − ligand, coordinated to rhodium. 86 This experimental assignment of the observed oxidation peaks, agrees with the character of the DFT calculated Kohn-Sham HOMO and HOMO−1 of the [Rh(FcCOCHCOR′)(cod)] complexes: the HOMO is mainly of rhodium d z 2 character and the HOMO−1 is mainly Febased; 74,87 (see Fig. 20).…”

Section: Dft and Electrochemical Oxidationsupporting

confidence: 79%

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Density functional theory calculations of Rh-β-diketonato complexes

Conradie

2015

Dalton Trans.

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Density functional theory (DFT) results on the geometry, energies and charges of selected Rh-β-diketonato reactants, products and transition states are discussed. Various DFT techniques are used to increase our understanding of the orientation of ligands coordinated to Rh, to identify the lowest energy geometry of possible geometrical isomers and to get a molecular orbital understanding of ground and transition states. Trends and relationships obtained between DFT calculated energies and charges, experimentally measured values and electronic parameters describing the electron donating power of groups and ligands, enable the design of ligands and complexes of specific reactivity.

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Section: Dft and Electrochemical Oxidationsupporting

confidence: 79%

“…the graph of E HOMO versus ln k 2 (substitution) will have a negative slope (see Fig. 16 74 and Fig. 17 75 ), which is contrary to the positive slope of the E HOMO versus ln k 2 (oxidative addition) graph (see Fig.…”

Section: Dft and Chemical Kinetics (For Oxidative Addition And Substi...mentioning

confidence: 92%

Density functional theory calculations of Rh-β-diketonato complexes

Conradie

2015

Dalton Trans.

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“…4, in green, red and blue respectively. Electronic parameters often used to describe the electron donating power of the b-diketone ligand or the R groups of the b-diketone on a metal it is coordinated to [34][35][36][37][38][39][40], are also tabulated in Table 3 The values obtained from literature [8] for Mn(CH 3 COCHCOFc) 3 (where Fc = ferrocenyl), complex (10), were also added to the graphs. The correlation of the mean of E pa and E pc of the Mn III /Mn II couple in Fig.…”

Section: Resultsmentioning

confidence: 99%