Linear relationships in α,β-unsaturated carbonyl compounds between the half-wave reduction potentials, the frontier orbital energies and the Hammett σp values

A tool for deciphering the redox potential ranking of organic compounds: a case study of biomass-extracted quinones for sustainable energy

“…At variance with the standard attempts to search for direct relationships between molecular redox potentials and frontier orbitals (i.e. the highest occupied molecular orbital, HOMO, or the lowest unoccupied molecular orbital, LUMO) 23,24,25,26,27,28,29 , or to empirically relating them to the substituent effects through the Hammett-Zuman model 30 , it is highly desirable to define a quantum chemical approach able to account for the electrochemical features while being at the same time fully independent of the nature of the This journal is © The Royal Society of Chemistry 20xx…”

Photoiodocarboxylation of Activated C═C Double Bonds with CO2 and Lithium Iodide

“…Substrates 1 and CO 2 are competitive scavengers of the photodetached electron from the iodide anion ( E ° red (aq/ e – aq ) = −3.11 V vs SCE) under our standard conditions, according to the data reported on the standard reduction potentials (Table ) − and the rate constants for the reaction with hydrated electrons (3.1 × 10 10 M –1 s –1 and 7.7 × 10 9 M –1 s –1 , for 1b and CO 2 , respectively). , The rate constants reported for selected reactions of acrylamide ( 1b ) from pulse radiolysis studies , are shown in Scheme . However, CO 2 has a singular competitive advantage over substrates 1 in acetonitrile solution as it actually resides in the solvation shell of the iodide anion.…”

Regioselective 1,4-Conjugate Addition of Grignard Reagents to α,β–γ,δ-Dienones and α,β–γ,δ-Dienyl Thiol Esters

“…6 Reduction potentials (i.e., E 1/2 ) vs the saturated calomel electrode (SCE) have been reported for Aa, Ba, C, and D (Figure 2). 31 A plot of relative % 1,4addition vs ΔE (Figure 2A) 32 shows a correlation coefficient of r = −0.63, while the plot of % 1,4-addition vs E 1/2 (Figure 2B) shows a correlation coefficient of r = 0.61, which are fairly strong correlations and particularly so when considering that the Grignard reagents likely to involve a carbanion mechanism are also included in the plot (i.e., PhMgX and MeMgX). It should be noted that correlation of E 1/2 with % 1,4-addition (Figure 2) is nearly the same as ΔE (i.e., ΔE = E o − E 1/2 ), and consequently, the correlation with E 1/2 (single property of substrate) is a simpler explanation than ΔE (two properties involving substrate and Grignard reagent) and following Occam's razor (law of parsimony) a more useful explanation (i.e., relies on fewer elements or components to explain the observation).…”