TY  - JOUR
AU  - Iali, Wissam
AU  - Petrovic, Predrag V.
AU  - Pfeffer, Michel
AU  - Grimme, Stefan
AU  - Djukic, Jean-Pierre
PY  - 2012
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/5372
AB  - A series of iridacycles bearing π-bonded moieties of variable electron-withdrawing capabilities were tested for their ability to promote water oxidation catalysis (WOC) in the presence of high loading in a sacrificial oxidant, under conditions chosen for optimal dioxygen production. This report shows that none of these complexes performs differently than monometallic iridacycles and that the π-bonded moiety does not affect the overall rate of O2 production. Furthermore, it is shown that cucurbituril macrocycles significantly inhibit the production of dioxygen independently of the nature of the Cp*Ir(III)-based catalyst used to perform WOC. Theoretical first-principles based DFT-D3 investigations including a complete treatment of solvation with COSMO and COSMO-RS treatments supported by ITC analyses suggest that concealment of the catalyst by curcurbit[7]uril could occur by non-covalent interaction of the Cp*Ir moiety in the hydrophobic pocket of the cavitand. For other cavitands of smaller inner cavity diameter, inclusion may not be the main mode of inhibition. Assuming the intervention of the putative Ir(IV)–oxyl biradical of a Cp*IrIV(O)(H2O)2 species like suggested by many authors, inhibition of WOC by inclusion would probably result from unfavourable coulombic interactions between water and the inclusion complex.
PB  - Royal Society of Chemistry
T2  - Dalton Transactions
T1  - The inhibition of iridium-promoted water oxidation catalysis (WOC) by cucurbit[n]urils
VL  - 41
SP  - 12233
DO  - 10.1039/C2DT31363D
ER  - 

@article{
author = "Iali, Wissam and Petrovic, Predrag V. and Pfeffer, Michel and Grimme, Stefan and Djukic, Jean-Pierre",
year = "2012",
abstract = "A series of iridacycles bearing π-bonded moieties of variable electron-withdrawing capabilities were tested for their ability to promote water oxidation catalysis (WOC) in the presence of high loading in a sacrificial oxidant, under conditions chosen for optimal dioxygen production. This report shows that none of these complexes performs differently than monometallic iridacycles and that the π-bonded moiety does not affect the overall rate of O2 production. Furthermore, it is shown that cucurbituril macrocycles significantly inhibit the production of dioxygen independently of the nature of the Cp*Ir(III)-based catalyst used to perform WOC. Theoretical first-principles based DFT-D3 investigations including a complete treatment of solvation with COSMO and COSMO-RS treatments supported by ITC analyses suggest that concealment of the catalyst by curcurbit[7]uril could occur by non-covalent interaction of the Cp*Ir moiety in the hydrophobic pocket of the cavitand. For other cavitands of smaller inner cavity diameter, inclusion may not be the main mode of inhibition. Assuming the intervention of the putative Ir(IV)–oxyl biradical of a Cp*IrIV(O)(H2O)2 species like suggested by many authors, inhibition of WOC by inclusion would probably result from unfavourable coulombic interactions between water and the inclusion complex.",
publisher = "Royal Society of Chemistry",
journal = "Dalton Transactions",
title = "The inhibition of iridium-promoted water oxidation catalysis (WOC) by cucurbit[n]urils",
volume = "41",
pages = "12233",
doi = "10.1039/C2DT31363D"
}

Iali, W., Petrovic, P. V., Pfeffer, M., Grimme, S.,& Djukic, J.. (2012). The inhibition of iridium-promoted water oxidation catalysis (WOC) by cucurbit[n]urils. in Dalton Transactions
Royal Society of Chemistry., 41, 12233.
https://doi.org/10.1039/C2DT31363D

Iali W, Petrovic PV, Pfeffer M, Grimme S, Djukic J. The inhibition of iridium-promoted water oxidation catalysis (WOC) by cucurbit[n]urils. in Dalton Transactions. 2012;41:12233.
doi:10.1039/C2DT31363D .

Iali, Wissam, Petrovic, Predrag V., Pfeffer, Michel, Grimme, Stefan, Djukic, Jean-Pierre, "The inhibition of iridium-promoted water oxidation catalysis (WOC) by cucurbit[n]urils" in Dalton Transactions, 41 (2012):12233,
https://doi.org/10.1039/C2DT31363D . .